Nitride semiconductor structure, nitride semiconductor light emitting element, nitride semiconductor transistor element, method of manufacturing nitride semiconductor structure, and method of manufacturing nitride semiconductor element

ABSTRACT

A nitride semiconductor structure in which a first nitride semiconductor underlying layer is provided on a substrate having a recess portion and a projection portion provided between the recess portions at a surface thereof, the first nitride semiconductor underlying layer has at least 6 first oblique facet planes surrounding the projection portion on an outer side of the projection portion, and a second nitride semiconductor underlying layer buries the first oblique facet planes, a nitride semiconductor light emitting element, a nitride semiconductor transistor element, a method of manufacturing a nitride semiconductor structure, and a method of manufacturing a nitride semiconductor element are provided.

REFERENCE TO RELATED APPLICATIONS

This application is a national stage application under 35 USC 371 ofInternational Application No. PCT/JP2011/079635, filed Dec. 21, 2011,which claims priority from Japanese Patent Application Nos. 2010-294413,filed Dec. 29, 2010, 2011-016496, filed Jan. 28, 2011, and 2011-066010,filed Mar. 24, 2011, the entire contents of which are incorporatedherein by reference.

FIELD OF THE INVENTION

The present invention relates to a nitride semiconductor structure, anitride semiconductor light emitting element, a nitride semiconductortransistor element, a method of manufacturing a nitride semiconductorstructure, and a method of manufacturing a nitride semiconductorelement.

BACKGROUND OF THE INVENTION

Since a group III-V compound semiconductor containing nitrogen (a groupIII nitride semiconductor) has a band gap corresponding to energy oflight having a wavelength in a range from infrared to ultraviolet, it isuseful as a material for a light emitting element emitting light havinga wavelength in a range from infrared to ultraviolet or for a lightreceiving element receiving light having a wavelength in that range.

In addition, since a group III nitride semiconductor has strong bondbetween atoms forming the group III nitride semiconductor, a highbreakdown voltage, and a high saturated electron velocity, it is usefulalso as a material for electronic devices such as transistors havingresistance to high temperature, achieving high output, and adapted to ahigh frequency.

Moreover, the group III nitride semiconductor has attracted attentionalso as a material which hardly adversely affects an environment and iseasy to handle.

In order to fabricate a practical nitride semiconductor element by usingthe group III nitride semiconductor which is an excellent material asdescribed above, a group III nitride semiconductor layer formed of thinfilms of the group III nitride semiconductor should be stacked on aprescribed substrate to thereby form a prescribed element structure.

Here, a substrate made of a group III nitride semiconductor having alattice constant and a coefficient of thermal expansion allowing directgrowth of the group III nitride semiconductor on the substrate is mostsuitably used as a substrate, and for example, a gallium nitride (GaN)substrate or the like is preferably used as a substrate made of thegroup III nitride semiconductor.

Currently, however, a GaN substrate is not practical because it has sucha small dimension as a diameter of 2 inches or smaller and it is alsovery expensive.

Therefore, under present circumstances, a sapphire substrate, a siliconcarbide (SiC) substrate, or the like, which is great in difference inlattice constant and coefficient of thermal expansion from the group IIInitride semiconductor, is used as a substrate for fabricating a nitridesemiconductor element.

The sapphire substrate and GaN which is a representative group IIInitride semiconductor are different from each other in lattice constantby approximately 16%. In addition, the SiC substrate and GaN aredifferent from each other in lattice constant by approximately 6%. Ifsuch a great difference in lattice constant is present between asubstrate and a group III nitride semiconductor grown thereon, it isgenerally difficult to epitaxially grow a crystal made of the group IIInitride semiconductor on the substrate. For example, when GaN crystal isepitaxially grown directly on a sapphire substrate, three-dimensionalgrowth of GaN crystal is inevitable and GaN crystal having a flatsurface cannot be obtained.

Then, what is called a buffer layer for eliminating a difference inlattice constant between a substrate and a group III nitridesemiconductor is generally formed between the substrate and the groupIII nitride semiconductor.

For example, PTL 1 (Japanese Patent No. 3026087) describes a method ofgrowing a group III nitride semiconductor composed of Al_(x)Ga_(1-x)Nafter a buffer layer composed of AlN is formed on a sapphire substratewith MOVPE.

With the method described in PTL 1, however, it has been difficult toobtain a buffer layer composed of AlN and having a flat surface withgood reproducibility. This may be because, in forming a buffer layercomposed of AlN with MOVPE, a trimethylaluminum (TMA) gas and an ammonia(NH₃) gas used as source material gases are likely to react to eachother in a vapor phase.

Therefore, with the method described in PTL 1, it has been difficult togrow a group III nitride semiconductor composed of high-qualityAl_(x)Ga_(1-x)N, having a flat surface, and having low defect density ona buffer layer composed of AlN with good reproducibility.

For example, PTL 2 (Japanese Patent Publication No. 5-86646) discloses amethod of forming on a sapphire substrate, an Al_(x)Ga_(1-x)N (0<x≦1)buffer layer with high-frequency sputtering in which a DC bias isapplied.

The group III nitride semiconductor formed on the Al_(x)Ga_(1-x)N(0<x≦1) buffer layer with the method described in PTL 2, however, didnot have excellent crystallinity as described in paragraph [0004] of PTL3 and paragraph [0004] of PTL 4.

Then, PTL 3 (Japanese Patent No. 3440873) has proposed a method ofsubjecting a buffer layer made of a group III nitride semiconductorformed with DC magnetron sputtering to heat treatment in an atmosphereof a gas mixture of a hydrogen gas and an ammonia gas. In addition, PTL4 (Japanese Patent No. 3700492) has proposed a method of forming abuffer layer made of a group III nitride semiconductor and having a filmthickness not smaller than 50 angstroms and not greater than 3000angstroms with DC magnetron sputtering on a sapphire substrate of whichtemperature was raised to 400° C. or higher.

Moreover, PTL 5 (Japanese Patent Laying-Open No. 2008-34444) hasproposed a method of forming a buffer layer composed of AlN columncrystals with high-frequency sputtering on a sapphire substrate heatedto 750° C.

Furthermore, PTL 6 (Japanese Patent No. 3950471) describes providingprojecting and recessed structures at a substrate surface in order togrow a group III nitride semiconductor having few crystal defects andlaterally growing the group III nitride semiconductor thereon.

Further, PTL 7 (Japanese Patent Laying-Open No. 2006-352084) describesin paragraphs [0043] and [0044], growth in two stages including the stepof growing a GaN layer on a substrate provided with projecting andrecessed structures that “a GaN layer 12 is grown in such a way as toform an isosceles triangle in section that has . . . a facet inclinedrelative to the main surface of the sapphire substrate 11,” and the stepthat “next, when the growth is continued while setting the conditionswhere lateral growth is predominant . . . GaN layer 12 is laterallygrown so that the surface of the GaN layer 12 creates a flat surface inparallel to the main surface of the sapphire substrate 11.”

-   PTL 1: Japanese Patent No. 3026087-   PTL 2: Japanese Patent Publication No. 5-86646-   PTL 3: Japanese Patent No. 3440873-   PTL 4: Japanese Patent No. 3700492-   PTL 5: Japanese Patent Laying-Open No. 2008-34444-   PTL 6: Japanese Patent No. 3950471-   PTL 7: Japanese Patent Laying-Open No. 2006-352084

SUMMARY OF THE INVENTION

Even in a case where a buffer layer made of a group III nitridesemiconductor is formed and a group III nitride semiconductor layer isformed on the buffer layer with the method described in PTLs 3 to 5above, the group III nitride semiconductor layer having excellentcrystallinity could not be formed with good reproducibility, andconsequently, a nitride semiconductor element having goodcharacteristics could not be fabricated with good reproducibility.

In addition, even in the case where a buffer layer made of a group IIInitride semiconductor is formed according to the method described in PTL5 above on a substrate including projections and recesses according tothe method described in PTL 6 above and a group III nitridesemiconductor layer is further formed with lateral growth described inPTL 7 above on that buffer layer, a group III nitride semiconductorlayer having aimed excellent crystallinity could not be formed with goodreproducibility.

Furthermore, as a size of a substrate becomes greater from 2 inches to 3inches, 4 inches, 6 inches, and 8 inches, it has been difficult to forma group III nitride semiconductor layer having excellent crystallinityuniformly in a substrate surface.

In view of the circumstances above, an object of the present inventionis to provide a nitride semiconductor structure allowing a nitride layerhaving excellent crystallinity to be formed in an upper portion thereofwith good reproducibility, a nitride semiconductor light emittingelement, a nitride semiconductor transistor element, a method ofmanufacturing a nitride semiconductor structure, and a method ofmanufacturing a nitride semiconductor element.

According to a first manner of the present invention, a nitridesemiconductor structure including a substrate having a recess portionand a projection portion provided between the recess portions at itssurface, a nitride semiconductor intermediate layer provided on thesubstrate, a first nitride semiconductor underlying layer provided onthe nitride semiconductor intermediate layer, and a second nitridesemiconductor underlying layer provided on the first nitridesemiconductor underlying layer, in which the substrate is composed oftrigonal corundum or hexagonal crystal, the first nitride semiconductorunderlying layer has at least 6 first oblique facet planes surroundingthe projection portion on an outer side of the projection portion, thesecond nitride semiconductor underlying layer has a lower surface incontact with the first oblique facet plane of the first nitridesemiconductor underlying layer, and the second nitride semiconductorunderlying layer has a flat upper surface, can be provided.

Here, in the nitride semiconductor structure according to the firstmanner of the present invention, preferably, the first oblique facetplane is inclined with respect to an m axis of a nitride semiconductorhaving a hexagonal structure.

In addition, in the nitride semiconductor structure according to thefirst manner of the present invention, preferably, the projectionportion is arranged along a <11-20> direction of the substrate.

In addition, in the nitride semiconductor structure according to thefirst manner of the present invention, preferably, in a cross-sectionalview passing through a center of the projection portion in a plan viewof the surface of the substrate, the projection portion is in a shapehaving a tip end portion.

In addition, in the nitride semiconductor structure according to thefirst manner of the present invention, preferably, the nitridesemiconductor intermediate layer is composed of a nitride semiconductorexpressed with a formula AlN or Al_(x)Ga_(1-x)N (0.5<x≦1).

In addition, in the nitride semiconductor structure according to thefirst manner of the present invention, preferably, the substrate is asapphire substrate.

In addition, according to the first manner of the present invention, anitride semiconductor light emitting element including any nitridesemiconductor structure described above, a first-conductivity-typenitride semiconductor layer provided on the nitride semiconductorstructure, a nitride semiconductor active layer provided on thefirst-conductivity-type nitride semiconductor layer, asecond-conductivity-type nitride semiconductor layer provided on thenitride semiconductor active layer, a first electrode in contact withthe first-conductivity-type nitride semiconductor layer, and a secondelectrode in contact with the second-conductivity-type nitridesemiconductor layer can be provided.

In addition, according to the first manner of the present invention, anitride semiconductor transistor element including any nitridesemiconductor structure described above, a first-conductivity-typenitride semiconductor electron transit layer provided on the nitridesemiconductor structure, a first-conductivity-type nitride semiconductorelectron supply layer provided on the first-conductivity-type nitridesemiconductor electron transit layer, and an electrode provided on thefirst-conductivity-type nitride semiconductor electron supply layer canbe provided.

In addition, according to the first manner of the present invention, anitride semiconductor structure including a sapphire substrate having arecess portion and a projection portion provided between the recessportions at a c plane or a surface inclined with respect to the c planein a range of 5° or smaller, a nitride semiconductor intermediate layerprovided on the sapphire substrate, a first nitride semiconductorunderlying layer provided on the recess portion with the nitridesemiconductor intermediate layer being interposed, and a second nitridesemiconductor underlying layer provided on the first nitridesemiconductor underlying layer, in which the projection portion isarranged along a <11-20> direction of the sapphire substrate, the firstnitride semiconductor underlying layer has a first oblique facet planesurrounding the projection portion on an outer side of the projectionportion, the second nitride semiconductor underlying layer has a lowersurface in contact with the first oblique facet plane of the firstnitride semiconductor underlying layer, and the second nitridesemiconductor underlying layer has a flat upper surface, can beprovided.

In addition, according to the first manner of the present invention, amethod of manufacturing a nitride semiconductor structure including thesteps of preparing a substrate composed of trigonal corundum orhexagonal crystal and having a c plane or a surface inclined withrespect to the c plane in a range of 5° or smaller, forming a recessportion and a projection portion provided between the recess portions atthe surface of the substrate, forming a nitride semiconductorintermediate layer on the surface of the substrate where the recessportion and the projection portion are formed, forming on the nitridesemiconductor intermediate layer, a first nitride semiconductorunderlying layer having at least 6 first oblique facet planessurrounding the projection portion on an outer side of the projectionportion with the projection portion being located in a center, andforming a second nitride semiconductor underlying layer on the firstnitride semiconductor underlying layer such that an upper surfacethereof is flat can be provided.

Here, in the method of manufacturing a nitride semiconductor structureaccording to the first manner of the present invention, preferably, thesteps of forming a first nitride semiconductor underlying layer andforming a second nitride semiconductor underlying layer are each agrowth step with MOCVD (Metal Organic Chemical Vapor Deposition), andthey are performed to satisfy at least one condition selected from thegroup consisting of

(i-1) setting a growth temperature during growth of the first nitridesemiconductor underlying layer to be lower than a growth temperatureduring growth of the second nitride semiconductor underlying layer,

(ii-1) setting a pressure during growth of the first nitridesemiconductor underlying layer to be higher than a pressure duringgrowth of the second nitride semiconductor underlying layer, and

(iii-1) setting a V/III ratio of a gas supplied during growth of thefirst nitride semiconductor underlying layer to be higher than a V/IIIratio of a gas supplied during growth of the second nitridesemiconductor underlying layer.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the first manner of the present invention,preferably, the nitride semiconductor intermediate layer is formed withsputtering.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the first manner of the present invention,preferably, the first oblique facet plane is a plane inclined withrespect to an m axis of a nitride semiconductor having a hexagonalstructure.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the first manner of the present invention,preferably, the projection portion is arranged along a <11-20> directionof the substrate.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the first manner of the present invention,preferably, in a cross-sectional view passing through a center of theprojection portion in a plan view of the surface of the substrate, theprojection portion is in a shape having a tip end portion.

Further, according to the first manner of the present invention, amethod of manufacturing a nitride semiconductor element including thesteps of preparing a substrate composed of trigonal corundum orhexagonal crystal and having a c plane or a surface inclined withrespect to the c plane in a range of 5° or smaller, forming a recessportion and a projection portion provided between the recess portions atthe surface of the substrate, forming a nitride semiconductorintermediate layer on the surface of the substrate where the recessportion and the projection portion are formed, forming on the nitridesemiconductor intermediate layer, a first nitride semiconductorunderlying layer having at least 6 first oblique facet planessurrounding the projection portion on an outer side of the projectionportion with the projection portion being located in a center, forming asecond nitride semiconductor underlying layer on the first nitridesemiconductor underlying layer such that an upper surface thereof isflat, and forming at least one nitride semiconductor layer on the secondnitride semiconductor underlying layer can be provided.

According to a second manner of the present invention, a nitridesemiconductor structure including a substrate having a recess portionand a projection portion provided between the recess portions at itssurface, a nitride semiconductor intermediate layer provided on thesubstrate, a third nitride semiconductor underlying layer provided onthe nitride semiconductor intermediate layer at least in the recessportion, a first nitride semiconductor underlying layer provided atleast on the third nitride semiconductor underlying layer, and a secondnitride semiconductor underlying layer provided at least on the firstnitride semiconductor underlying layer, in which the substrate iscomposed of trigonal corundum or hexagonal crystal, a surface of thethird nitride semiconductor underlying layer has a third oblique facetplane and a third flat region, a ratio of area of the third obliquefacet plane at the surface of the third nitride semiconductor underlyinglayer is lower than a ratio of area of the third flat region, the firstnitride semiconductor underlying layer has a first oblique facet planesurrounding the projection portion, the second nitride semiconductorunderlying layer has a lower surface in contact with the first obliquefacet plane, and the second nitride semiconductor underlying layer has aflat upper surface, can be provided.

Here, in the nitride semiconductor structure according to the secondmanner of the present invention, preferably, the first oblique facetplane includes a plane inclined with respect to an m axis of a nitridesemiconductor having a hexagonal structure.

In addition, in the nitride semiconductor structure according to thesecond manner of the present invention, preferably, the projectionportion is arranged along a <11-20> direction of the substrate.

In addition, in the nitride semiconductor structure according to thesecond manner of the present invention, preferably, in a cross-sectionalview passing through a center of the projection portion in a plan viewof the surface of the substrate, the projection portion is in a shapehaving a tip end portion.

In addition, in the nitride semiconductor structure according to thesecond manner of the present invention, preferably, the nitridesemiconductor intermediate layer is composed of a nitride semiconductorexpressed with a formula AlN or Al_(x)Ga_(1-x)N (0.5<x≦1).

In addition, in the nitride semiconductor structure according to thesecond manner of the present invention, preferably, the substrate is asapphire substrate.

In addition, according to the second manner of the present invention, anitride semiconductor structure including a sapphire substrate having arecess portion and a projection portion provided between the recessportions at a c plane or a surface inclined with respect to the c planein a range of 5° or smaller, a nitride semiconductor intermediate layerprovided on the sapphire substrate, a third nitride semiconductorunderlying layer provided on the nitride semiconductor intermediatelayer at least in the recess portion, a first nitride semiconductorunderlying layer provided at least on the third nitride semiconductorunderlying layer, and a second nitride semiconductor underlying layerprovided at least on the first nitride semiconductor underlying layer,in which the projection portion is arranged along a <11-20> direction ofthe sapphire substrate, a surface of the third nitride semiconductorunderlying layer has a third oblique facet plane and a third flatregion, a ratio of area of the third oblique facet plane at the surfaceof the third nitride semiconductor underlying layer is lower than aratio of area of the third flat region, the first nitride semiconductorunderlying layer has a first oblique facet plane surrounding theprojection portion and a first flat region, a ratio of area of the firstoblique facet plane in a plan view of the first nitride semiconductorunderlying layer is higher than a ratio of area of the first flatregion, the second nitride semiconductor underlying layer has a lowersurface in contact with the first oblique facet plane, and the secondnitride semiconductor underlying layer has a flat upper surface, can beprovided.

In addition, according to the second manner of the present invention, anitride semiconductor light emitting element including any nitridesemiconductor structure described above, a first-conductivity-typenitride semiconductor layer provided on the nitride semiconductorstructure, a nitride semiconductor light emitting layer provided on thefirst-conductivity-type nitride semiconductor layer, asecond-conductivity-type nitride semiconductor layer provided on thenitride semiconductor light emitting layer, a first electrode in contactwith the first-conductivity-type nitride semiconductor layer, and asecond electrode in contact with the second-conductivity-type nitridesemiconductor layer, can be provided.

In addition, according to the second manner of the present invention, anitride semiconductor transistor element including any nitridesemiconductor structure described above, a first-conductivity-typenitride semiconductor electron transit layer provided on the nitridesemiconductor structure, a first-conductivity-type nitride semiconductorelectron supply layer provided on the first-conductivity-type nitridesemiconductor electron transit layer, and an electrode provided on thefirst-conductivity-type nitride semiconductor electron supply layer, canbe provided.

In addition, according to the second manner of the present invention, amethod of manufacturing a nitride semiconductor structure including thesteps of preparing a substrate composed of trigonal corundum orhexagonal crystal and having a c plane or a surface inclined withrespect to the c plane in a range of 5° or smaller, forming a recessportion and a projection portion provided between the recess portions atthe surface of the substrate, forming a nitride semiconductorintermediate layer on the surface of the substrate where the recessportion and the projection portion are formed, forming a third nitridesemiconductor underlying layer on the nitride semiconductor intermediatelayer at least in the recess portion, forming a first nitridesemiconductor underlying layer at least on the third nitridesemiconductor underlying layer, and forming a second nitridesemiconductor underlying layer at least on the first nitridesemiconductor underlying layer, in which the step of forming a thirdnitride semiconductor underlying layer is performed under such acondition that a surface of the third nitride semiconductor underlyinglayer has a third oblique facet plane and a third flat region and aratio of area of the third oblique facet plane at the surface of thethird nitride semiconductor underlying layer is lower than a ratio ofarea of the third flat region, the step of forming a first nitridesemiconductor underlying layer is performed under such a condition thata first oblique facet plane surrounding the projection portion isformed, and the step of forming a second nitride semiconductorunderlying layer is performed under such a condition that a lowersurface of the second nitride semiconductor underlying layer is incontact with the first oblique facet plane and an upper surface of thesecond nitride semiconductor underlying layer is flat, can be provided.

Here, in a method of manufacturing a nitride semiconductor structureaccording to the second manner of the present invention, preferably, thestep of forming a third nitride semiconductor underlying layer isperformed under such a condition that a ratio of area of a rough surfaceregion at the surface of the third nitride semiconductor underlyinglayer is not higher than 5%.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the second manner of the present invention,preferably, the step of forming a third nitride semiconductor underlyinglayer and a first nitride semiconductor underlying layer is performed tosatisfy at least one condition selected from the group consisting of(i-2) setting a growth temperature during growth of the third nitridesemiconductor underlying layer to be higher than a growth temperatureduring growth of the first nitride semiconductor underlying layer,(ii-2) setting a pressure during growth of the third nitridesemiconductor underlying layer to be lower than a pressure during growthof the first nitride semiconductor underlying layer, and (iii-2) settinga V/III ratio of a gas supplied during growth of the third nitridesemiconductor underlying layer to be lower than a V/III ratio of a gassupplied during growth of the first nitride semiconductor underlyinglayer.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the second manner of the present invention,preferably, the step of forming a third nitride semiconductor underlyinglayer, a first nitride semiconductor underlying layer, and a secondnitride semiconductor underlying layer is performed to satisfy at leastone condition selected from the group consisting of (I-3) setting agrowth temperature during growth of the second nitride semiconductorunderlying layer to be higher than a growth temperature during growth ofthe third nitride semiconductor underlying layer, (II-3) setting apressure during growth of the second nitride semiconductor underlyinglayer to be lower than a pressure during growth of the third nitridesemiconductor underlying layer, and (III-3) setting a V/III ratio of agas supplied during growth of the second nitride semiconductorunderlying layer to be lower than a V/III ratio of a gas supplied duringgrowth of the third nitride semiconductor underlying layer, and isperformed to satisfy at least one condition selected from the groupconsisting of (a-3) setting a growth temperature during growth of thesecond nitride semiconductor underlying layer to be higher than a growthtemperature during growth of the first nitride semiconductor underlyinglayer, (b-3) setting a pressure during growth of the second nitridesemiconductor underlying layer to be lower than a pressure during growthof the first nitride semiconductor underlying layer, and (c-3) setting aV/III ratio of a gas supplied during growth of the second nitridesemiconductor underlying layer to be lower than a V/III ratio of a gassupplied during growth of the first nitride semiconductor underlyinglayer.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the second manner of the present invention,preferably, the nitride semiconductor intermediate layer is formed withsputtering.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the second manner of the present invention,preferably, the first oblique facet plane includes a plane inclined withrespect to an m axis of a nitride semiconductor having a hexagonalstructure.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the second manner of the present invention,preferably, the projection portion is arranged along a <11-20> directionof the substrate.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the second manner of the present invention,preferably, in a cross-sectional view passing through a center of theprojection portion in a plan view of the surface of the substrate, theprojection portion is in a shape having a tip end portion.

Further, according to the second manner of the present invention, amethod of manufacturing a nitride semiconductor element including thesteps of forming any nitride semiconductor structure described above andforming at least one nitride semiconductor layer on the nitridesemiconductor structure can be provided.

In addition, according to a third manner of the present invention, amethod of manufacturing a nitride semiconductor structure including thesteps of preparing a substrate having a recess portion and a projectionportion provided between the recess portions at its surface, forming anitride semiconductor intermediate layer on the substrate, and formingon the nitride semiconductor intermediate layer, a first nitridesemiconductor underlying layer having at least 6 first oblique facetplanes surrounding the projection portion on an outer side of theprojection portion with the projection portion being located in acenter, in which the step of forming a first nitride semiconductorunderlying layer includes the step of growing the first nitridesemiconductor underlying layer with MOCVD by using a vertical MOCVDapparatus in which a carrier gas containing a hydrogen gas is used whilethe substrate is rotated, the number of rotations of the substrate perunit time is not lower than 400 RPM and not higher than 1000 RPM, and avolume ratio of the hydrogen gas with respect to a total volume of thecarrier gas is not lower than 0.7 and not higher than 1, can beprovided.

Here, preferably, the method of manufacturing a nitride semiconductorstructure according to the third manner of the present invention furtherincludes the step of forming a second nitride semiconductor underlyinglayer on the first nitride semiconductor underlying layer, and the stepsof forming a first nitride semiconductor underlying layer and forming asecond nitride semiconductor underlying layer are each the step ofgrowing the first nitride semiconductor underlying layer and the secondnitride semiconductor underlying layer with MOCVD in which a carrier gascontaining a hydrogen gas is used while the substrate is rotated, andperformed to satisfy at least one condition selected from the groupconsisting of

(i-3) setting a growth temperature during growth of the first nitridesemiconductor underlying layer to be lower than a growth temperatureduring growth of the second nitride semiconductor underlying layer,

(ii-3) setting a pressure during growth of the first nitridesemiconductor underlying layer to be higher than a pressure duringgrowth of the second nitride semiconductor underlying layer,

(iii-3) setting a V/III ratio of a source material gas supplied duringgrowth of the first nitride semiconductor underlying layer to be higherthan a V/III ratio of a source material gas supplied during growth ofthe second nitride semiconductor underlying layer, (iv-3) setting thenumber of rotations of the substrate per unit time during growth of thefirst nitride semiconductor underlying layer to be smaller than thenumber of rotations of the substrate per unit time during growth of thesecond nitride semiconductor underlying layer, and (v-3) setting avolume ratio of the hydrogen gas with respect to the total volume of thecarrier gas during growth of the first nitride semiconductor underlyinglayer to be equal to or higher than a volume ratio of the hydrogen gaswith respect to the total volume of the carrier gas during growth of thesecond nitride semiconductor underlying layer.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the third manner of the present invention,preferably, the step of preparing a substrate includes the step offorming the projection portion and the recess portion at a c plane ofthe substrate or a surface inclined with respect to the c plane in arange of 5° or smaller.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the third manner of the present invention,preferably, the substrate is composed of trigonal corundum or hexagonalcrystal.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the third manner of the present invention,preferably, the projection portion is arranged along a <11-20> directionof the substrate.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the third manner of the present invention,preferably, in a cross-sectional view passing through a center of theprojection portion in a plan view of the surface of the substrate, theprojection portion is in a shape having a tip end portion.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the third manner of the present invention,preferably, the step of forming a nitride semiconductor intermediatelayer includes the step of forming the nitride semiconductorintermediate layer with sputtering.

In addition, in the method of manufacturing a nitride semiconductorstructure according to the third manner of the present invention,preferably, the nitride semiconductor intermediate layer is composed ofa nitride semiconductor expressed with a formula AlN or Al_(x)Ga_(1-x)N(0.5<x≦1).

Further, according to the third manner of the present invention, amethod of manufacturing a nitride semiconductor element including thestep of forming a nitride semiconductor layer on a surface of the secondnitride semiconductor underlying layer manufactured with the method ofmanufacturing a nitride semiconductor structure described above can beprovided.

According to the present invention, a nitride semiconductor structureallowing a nitride layer having excellent crystallinity to be formed inan upper portion thereof with good reproducibility, a nitridesemiconductor light emitting element, a nitride semiconductor transistorelement, a method of manufacturing a nitride semiconductor structure,and a method of manufacturing a nitride semiconductor element can beprovided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of a nitride semiconductorlight emitting diode element in an embodiment.

FIG. 2 is a schematic cross-sectional view illustrating a part of stepsin one example of a method of manufacturing a nitride semiconductorlight emitting diode element in the embodiment.

FIG. 3 is a schematic enlarged plan view of one example of a surface ofa substrate shown in FIG. 2.

FIG. 4 is a schematic enlarged cross-sectional view along the line B-Bpassing through the center of a projection portion shown in FIG. 3.

FIG. 5 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 6 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 7 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 8 is a schematic enlarged plan view of one example of a surface ofa first nitride semiconductor underlying layer shown in FIG. 6.

FIG. 9 is a schematic enlarged plan view of another example of thesurface of the first nitride semiconductor underlying layer shown inFIG. 6.

FIG. 10 is a schematic enlarged plan view of another example of thesurface of the first nitride semiconductor underlying layer shown inFIG. 6.

FIG. 11 is a schematic enlarged plan view of another example of thesurface of the first nitride semiconductor underlying layer shown inFIG. 6.

FIG. 12 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 13 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 14 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 15 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 16 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 17 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 18 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 19 is a schematic cross-sectional view illustrating another part ofsteps in one example of the method of manufacturing a nitridesemiconductor light emitting diode element in the embodiment.

FIG. 20 is a schematic cross-sectional view of one example of a lightemitting device including the nitride semiconductor light emitting diodeelement in the embodiment.

FIG. 21 is a schematic cross-sectional view of a nitride semiconductortransistor element in an embodiment.

FIG. 22 is a schematic cross-sectional view of a nitride semiconductorlight emitting diode element in an embodiment.

FIG. 23 is a schematic cross-sectional view illustrating another part ofmanufacturing steps in one example of a method of manufacturing anitride semiconductor light emitting diode element in the embodiment.

FIG. 24 is a schematic cross-sectional view illustrating another part ofthe manufacturing steps in one example of the method of manufacturing anitride semiconductor light emitting diode element in the embodiment.

FIG. 25 is a schematic cross-sectional view illustrating another part ofthe manufacturing steps in one example of the method of manufacturing anitride semiconductor light emitting diode element in the embodiment.

FIG. 26 is a schematic cross-sectional view illustrating another part ofthe manufacturing steps in one example of the method of manufacturing anitride semiconductor light emitting diode element in the embodiment.

FIG. 27 is a schematic cross-sectional view of one example of a waferafter each layer of the nitride semiconductor underlying layer in theembodiment is formed.

FIG. 28 is a schematic cross-sectional view of one example of the waferafter each layer of the nitride semiconductor underlying layer in theembodiment is formed.

FIG. 29 is a schematic enlarged plan view of one example of a surface ofa third nitride semiconductor underlying layer.

FIG. 30 is a schematic enlarged plan view of another example of thesurface of the third nitride semiconductor underlying layer.

FIG. 31 is a schematic cross-sectional view along B-B in FIG. 30.

FIG. 32 is a schematic enlarged plan view of another example of thesurface of the third nitride semiconductor underlying layer.

FIG. 33 is a schematic enlarged plan view of one example of the surfaceof the first nitride semiconductor underlying layer grown after thethird nitride semiconductor underlying layer is formed.

FIG. 34 is a schematic cross-sectional view along B-B in FIG. 33.

FIG. 35 is a schematic enlarged plan view of another example of thesurface of the first nitride semiconductor underlying layer grown afterthe third nitride semiconductor underlying layer is formed.

FIG. 36 is a schematic cross-sectional view of one example of a lightemitting device including the nitride semiconductor light emitting diodeelement in the embodiment.

FIG. 37 is a schematic cross-sectional view of a nitride semiconductortransistor element in an embodiment.

FIG. 38 is a schematic cross-sectional view illustrating a part ofmanufacturing steps in a method of manufacturing a nitride semiconductorstructure in an embodiment.

FIG. 39 is a schematic cross-sectional view illustrating another part ofthe manufacturing steps in the method of manufacturing a nitridesemiconductor structure in the embodiment.

FIG. 40 is a schematic cross-sectional view of a nitride semiconductorlight emitting diode element in an embodiment.

FIG. 41 is a schematic cross-sectional view of a light emitting devicein an embodiment.

FIG. 42 is a schematic cross-sectional view of a nitride semiconductortransistor element in an embodiment.

FIG. 43 shows an SEM image of a surface of a third nitride semiconductorunderlying layer grown on a surface of a wafer of Sample 1.

FIG. 44 shows an SEM image of a surface of a third nitride semiconductorunderlying layer grown on a surface of a wafer of Sample 2.

FIG. 45 shows an SEM image of a surface of a third nitride semiconductorunderlying layer grown on a surface of a wafer of Sample 3.

FIG. 46 shows an SEM image of a surface of a third nitride semiconductorunderlying layer grown on a surface of a wafer of Sample 4.

FIG. 47 shows an SEM image of a surface of a third nitride semiconductorunderlying layer grown on a surface of a wafer of Sample 5.

FIG. 48 shows an SEM image of a surface of a third nitride semiconductorunderlying layer grown on a surface of a wafer of Sample 6.

FIG. 49 is a diagram showing relation between a growth temperature T₁ ofa third nitride semiconductor underlying layer and a half width (arcsec)of XRC at a GaN (004) plane which is an upper surface of a secondnitride semiconductor underlying layer.

FIG. 50 is a diagram showing relation between a growth temperature T₁ (°C.) of a third nitride semiconductor underlying layer and warpage (μm)of a wafer during growth of a second nitride semiconductor underlyinglayer.

FIG. 51 shows an SEM image of a surface of a first nitride semiconductorunderlying layer in an early stage of growth in Example 1.

FIG. 52 shows an SEM image of the surface of the first nitridesemiconductor underlying layer after growth in Example 1.

FIG. 53 shows an SEM image of a surface of a first nitride semiconductorunderlying layer in an early stage of growth in Comparative Example 1.

FIG. 54 shows an SEM image of the surface of the first nitridesemiconductor underlying layer after growth in Comparative Example 1.

FIG. 55 shows an SEM image of a surface of a first nitride semiconductorunderlying layer after growth in Comparative Example 2.

DETAILED DESCRIPTION OF THE INVENTION

An embodiment of the present invention will be described below. It isnoted that the same or corresponding portions have the same referencecharacters allotted in the drawings of the present invention.

<Crystal Orientation of Sapphire Substrate and Nitride SemiconductorCrystal>

A crystal system of (AlGaIn)N-based nitride semiconductor crystal isnormally hexagonal, and a crystal system of sapphire is trigonalcorundum, which, however, can be denoted with a hexagonal notationmethod. Then, regarding any of a sapphire substrate and a nitridesemiconductor crystal, a direction of a c axis is denoted as [0001], adirection of an a1 axis is denoted as [−2110], a direction of an a2 axisis denoted as [1-210], a direction of an a3 axis is denoted as [11-20],and three directions of the direction of the a1 axis, the direction ofthe a2 axis, and the direction of the a3 axis are collectively denotedas a direction of an a axis or a <11-20> direction. In addition, threedirections perpendicular to and equivalent to the direction of the caxis and the <11-20> direction are denoted as a direction of an m axis(most representatively, a <1-100> direction).

In denoting a crystal plane and a direction, they should essentially beexpressed with a required number with a bar thereabove. Means forexpression, however, is restricted, and hence a crystal plane and adirection are herein expressed with a required number preceded by “−”,instead of an expression with a required number with a bar thereabove.For example, according to the crystallographic notation, an oppositedirection of 1 should be denoted as 1 with a bar thereabove, however, itis denoted as “−1” for the sake of convenience.

Since there is a case where a direction of crystal of a substrate and adirection of crystal of a nitride semiconductor layer on the substrateare different from each other, attention should be paid to relationbetween a crystallographic axis of the substrate and a crystallographicaxis of the nitride semiconductor layer. It is assumed herein that adirection of crystal of a substrate is denoted together with “sub”, anda direction of crystal of a nitride semiconductor layer is denotedtogether with “layer”. For example, in a case where a substrate is madeof sapphire single crystal, a direction of an a (sub) axis of thesubstrate matches with a direction of an m (layer) axis of a nitridesemiconductor layer, and a direction of an m (sub) axis of the substratematches with a direction of an a (layer) axis of the nitridesemiconductor layer. On the other hand, in a case where a substrate iscomposed of AlN single crystal or GaN single crystal, a direction of ana (sub) axis of the substrate matches with a direction of an a (layer)axis of a nitride semiconductor layer, and a direction of an m (sub)axis of the substrate matches with a direction of an m (layer) axis ofthe nitride semiconductor layer.

<Wafer>

A “wafer” herein refers to a substrate before division or a substratebefore division on which each nitride semiconductor layer, an electrode,or other element necessary for a nitride semiconductor element has beenformed.

<Warpage>

Then, “warpage” of a wafer herein is defined. “Warpage” of a wafer ismainly caused by stress originating from difference in rate of thermalexpansion between a substrate and each nitride semiconductor layer.Here, a surface on a side where a nitride semiconductor layer is formedis defined as an upper surface of a wafer and a surface on a side wherea nitride semiconductor layer is not formed is defined as a lowersurface of the wafer. Then, a case where the wafer is warped in a shapeconvex on an upper surface side and a case where the wafer is warped ina shape convex on a lower surface side will be considered.

In the case where the wafer is warped in a shape convex on the uppersurface side, an amount of warpage of the wafer is expressed by amaximum value of an interval (difference in height) between the lowersurface of the wafer and a mount surface in a direction perpendicular toa flat surface when the wafer is mounted on the flat surface with itsupper surface facing upward and the lower surface facing the flatsurface, and a sign thereof is set to positive.

On the other hand, when the wafer is warped in a shape convex on thelower surface side, an amount of warpage of the wafer is expressed by amaximum value of an interval (difference in height) between the uppersurface of the wafer and a virtual plane in contact with a periphery ofthe upper surface of the wafer in the direction perpendicular to theflat surface with its upper surface facing upward and the lower surfacefacing the flat surface, and a sign thereof is set to negative.

It is noted that magnitude of warpage of the wafer is also dependent ona wafer diameter, and as the wafer is greater in diameter, warpage ofthe wafer is greater. In particular, since breakage of a wafer due towarpage of the wafer is likely in a large-diameter wafer having a waferdiameter not smaller than approximately 4 inches, it is also importantthat the wafer is free of breakage. In addition, no crack is preferablycaused in the surface of the wafer after each nitride semiconductorlayer is grown on the substrate.

Furthermore, magnitude of warpage of the wafer is also dependent on athickness of the substrate. For example, a sapphire substrate having a4-inch diameter has a thickness of 0.9 mm, and a sapphire substratehaving a 6-inch diameter has a thickness of 1.3 mm.

An amount of warpage of a wafer on which a nitride semiconductor layeris formed is preferably small to such an extent that a photolithographystep, a grinding and polishing step, or the like can be performedwithout problems.

<Evaluation Method>

Crystallinity of a nitride semiconductor layer can be evaluated based ona half width of an X-ray rocking curve, such as a half width of an X-rayrocking curve at a GaN (004) plane (equal to a (0004) plane in hexagonaldenotation). A smaller half width of an X-ray rocking curve indicatesbeing close to single crystal, which is preferred. It is assumed hereinthat a half width of an X-ray rocking curve indicates a value measuredat a wafer central portion, unless otherwise specified.

A crystal defect in a nitride semiconductor layer can be evaluated witha cathode luminescence (CL) method, etch pit density (EPD), or the like.Lower density of crystal defects indicates better crystallinity, whichis preferred.

Embodiment 1-1

FIG. 1 shows a schematic cross-sectional view of a nitride semiconductorlight emitting diode element in Embodiment 1-1 representing one exampleof a nitride semiconductor element according to the present invention.

A nitride semiconductor light emitting diode element 100 according toEmbodiment 1-1 includes a substrate 1, a nitride semiconductorintermediate layer 2 provided in contact with a surface of substrate 1,a first nitride semiconductor underlying layer 4 provided in contactwith a surface of nitride semiconductor intermediate layer 2, a secondnitride semiconductor underlying layer 5 provided in contact with asurface of each of nitride semiconductor intermediate layer 2 and firstnitride semiconductor underlying layer 4, an n-type nitridesemiconductor contact layer 7 provided in contact with a surface ofsecond nitride semiconductor underlying layer 5, an n-type nitridesemiconductor clad layer 9 provided in contact with a surface of n-typenitride semiconductor contact layer 7, a nitride semiconductor activelayer 11 provided in contact with a surface of n-type nitridesemiconductor clad layer 9, a p-type nitride semiconductor clad layer 13provided in contact with a surface of nitride semiconductor active layer11, a p-type nitride semiconductor contact layer 15 provided in contactwith a surface of p-type nitride semiconductor clad layer 13, and alight transmitting electrode layer 19 provided in contact with a surfaceof p-type nitride semiconductor contact layer 15.

Nitride semiconductor light emitting diode element 100 includes ann-side electrode 20 provided in contact with an exposed surface ofn-type nitride semiconductor contact layer 7 and a p-side electrode 21provided in contact with a surface of light transmitting electrode layer19.

The surface of light transmitting electrode layer 19 and an exposed endsurface of each of p-type nitride semiconductor contact layer 15, p-typenitride semiconductor clad layer 13, nitride semiconductor active layer11, n-type nitride semiconductor clad layer 9, and n-type nitridesemiconductor contact layer 7 are covered with an insulating protectionfilm 23 composed of SiO₂ or the like.

Substrate 1 is composed of trigonal corundum or hexagonal crystal, andit has at its

surface, a recess portion 1 b and a projection portion 1 a providedbetween recess portions 1 b.

First nitride semiconductor underlying layer 4 has at least 6 firstoblique facet planes 4 r surrounding projection portion 1 a on an outerside of projection portion 1 a of substrate 1 and has an upper surface 4c.

Second nitride semiconductor underlying layer 5 has a lower surface 5 bin contact with first oblique facet plane 4 r of first nitridesemiconductor underlying layer 4 and has a flat upper surface 5 a. Aconcept “flat” herein encompasses not only a case where upper surface 5a of second nitride semiconductor underlying layer 5 is completely flatbut also a case where upper surface 5 a of second nitride semiconductorunderlying layer 5 is substantially flat. For example, flat uppersurface 5 a of second nitride semiconductor underlying layer 5 hassurface roughness Ra (JIS B 0601:2001) not greater than 0.1 μm.

One example of a method of manufacturing nitride semiconductor lightemitting diode element 100 according to Embodiment 1-1 will be describedbelow.

Initially, substrate 1 composed of trigonal corundum or hexagonalcrystal is prepared. For example, a substrate made of sapphire (Al₂O₃)single crystal, AlN single crystal, GaN single crystal, or the like canbe employed as substrate 1 composed of trigonal corundum or hexagonalcrystal.

A main surface of substrate 1 (a surface before projection portion 1 aand recess portion 1 b are formed) may be a c plane or a surfaceinclined with respect to the c plane by 5° or smaller, and a directionof inclination may be, for example, only in a direction of the m (sub)axis (<1-100>), only in a direction of the a (sub) axis (<11-20>), or ina direction which is combination of both of these directions. Morespecifically, such a substrate that a main surface of substrate 1 (asurface before projection portion 1 a and recess portion 1 b are formed)is inclined by 0.15° to 0.35° in the direction of the m (sub) axis<1-100> of the substrate with respect to the c plane (a plane of whichnormal is the c axis) or the like can be prepared as substrate 1.

Though a diameter of substrate 1 is not particularly limited, forexample, it can be 150 mm (approximately 6 inches). Though a substratehaving a diameter around 50.8 mm (2 inches) has conventionally generallybeen employed as substrate 1, a substrate having a large diameter ispreferably employed for higher productivity. In a case of usingsubstrate 1 having a large diameter, however, breakage of substrate 1 ora crack in a surface of a nitride semiconductor layer is more likelybecause strain is accumulated after a nitride semiconductor layer isformed on substrate 1. As will be described later, the present inventioncan suppress breakage of substrate 1 or a crack caused in a surface of anitride semiconductor layer even in a case of using substrate 1 having alarge diameter not smaller than 100 mm (approximately 4 inches).

Then, as shown in a schematic cross-sectional view in FIG. 2, recessportion 1 b and projection portion 1 a provided between recess portions1 b are formed at the surface of substrate 1. Such projection portions 1a and recess portions 1 b at the surface of substrate 1 can be formed,for example, through a patterning step of forming a mask definingtwo-dimensional arrangement of projection portions 1 a on substrate 1and a step of forming recess portions 1 b by etching the surface ofsubstrate 1 with the use of the mask formed in the patterning step.Here, the patterning step can be performed with a commonphotolithography step. An etching step can be performed, for example,with dry etching or wet etching. In order that a shape of projectionportion 1 a has a tip end portion which will be described later,however, dry etching with which a shape of projection portion 1 a isreadily controlled is preferably carried out.

FIG. 3 shows a schematic enlarged plan view of one example of thesurface of substrate 1 shown in FIG. 2. In the plan view of the surfaceof substrate 1 shown in FIG. 3, projection portion 1 a having an annulartwo-dimensional shape is located, for example, at each vertex of avirtual triangle 1 t, and arranged in a direction of each of three sidesof virtual triangle 1 t. In the present example, projection portion 1 ais arranged in the direction of the a (sub) axis (<11-20> direction) ofthe surface of substrate 1, and arranged in a direction inclined by +60°with respect to the direction of the a (sub) axis of the surface ofsubstrate 1 and in a direction inclined by −60° with respect to thedirection of the a (sub) axis of the surface of substrate 1. It is notedherein that, in the plan view of the surface of substrate 1, thedirection inclined by +60° with respect to the direction of the a (sub)axis and the direction inclined by −60° with respect to the direction ofthe a (sub) axis are both referred to as a u direction.

It is noted that a center of an annular circle which is atwo-dimensional shape of projection portion 1 a does not necessarilyhave to completely match with a vertex of triangle 1 t and it shouldonly substantially match therewith. Specifically, if a center of acircle is displaced by a radius of that circle or less, first nitridesemiconductor underlying layer 4 tends to start growth on a region ofrecess portion 1 b in a manner more stable than on a region ofprojection portion 1 a. Then, as first nitride semiconductor underlyinglayer 4 further grows, first nitride semiconductor underlying layer 4tends to be able to form at least 6 first oblique facet planes 4 r so asto surround projection portion 1 a on an outer side of projectionportion 1 a with projection portion 1 a being located in the center.

A two-dimensional shape at a bottom surface of projection portion 1 a isnot limited to an annular shape, and it may be, for example, a polygonalshape such as a hexagonal and/or triangular shape.

In addition, in the plan view of the surface of substrate 1, an angle ofeach interior angle of virtual triangle 1 t where projection portion 1 ais arranged at each vertex is preferably not smaller than 50° and notgreater than 70°. In this case, first nitride semiconductor underlyinglayer 4 tends to start growth on the region of recess portion 1 b in amanner more stable than on the region of projection portion 1 a. Then,as first nitride semiconductor underlying layer 4 further grows, firstnitride semiconductor underlying layer 4 tends to be able to form atleast 6 first oblique facet planes 4 r so as to surround projectionportion 1 a on the outer side of projection portion 1 a with projectionportion 1 a being located in the center.

Moreover, in the plan view of the surface of substrate 1, an intervalbetween adjacent projection portions 1 a is preferably not smaller than0.2 μm and not greater than 7 μm and more preferably not smaller than 1μm and not greater than 3 μm. When an interval between adjacentprojection portions 1 a is not smaller than 0.2 μm and not greater than7 μm, a problem in terms of process tends to be less. The problem interms of process includes, for example, a longer time period of dryetching for increasing a height of projection portion 1 a, anexcessively long time period of growth required until upper surface 5 aof second nitride semiconductor underlying layer 5 is completely flat,and the like. It is noted herein that an interval between adjacentprojection portions 1 a means a shortest distance between adjacentprojection portions 1 a.

In the plan view of the surface of substrate 1, a diameter of an annularcircle of projection portion 1 a is preferably not smaller than ½ andnot greater than ¾ of an interval between adjacent projection portions 1a. For example, when an interval between adjacent projection portions 1a is 2 μm, a diameter of an annular circle of projection portion 1 a ismore preferably around 1.2 μm. When a diameter of an annular circle ofprojection portion 1 a is not smaller than ½ and not greater than ¾ ofan interval between adjacent projection portions 1 a and in particulararound 1.2 μm, first nitride semiconductor underlying layer 4 tends tostart growth on the region of recess portion 1 b in a manner more stablethan on the region of projection portion 1 a. Then, as first nitridesemiconductor underlying layer 4 further grows, first nitridesemiconductor underlying layer 4 tends to be able to form at least 6first oblique facet planes 4 r so as to surround projection portion 1 aon the outer side of projection portion 1 a with projection portion 1 abeing located in the center.

Furthermore, a height of projection portion 1 a is preferably notsmaller than ¼ and not greater than 1 of a diameter of an annular circleof projection portion 1 a. For example, when a diameter of an annularcircle of projection portion 1 a is 1.2 μm, a height of projectionportion 1 a is more preferably around 0.6 μm. In this case, firstnitride semiconductor underlying layer 4 tends to start growth on theregion of recess portion 1 b in a manner more stable than on the regionof projection portion 1 a. Then, as first nitride semiconductorunderlying layer 4 further grows, first nitride semiconductor underlyinglayer 4 tends to be able to form at least 6 first oblique facet planes 4r so as to surround projection portion 1 a on the outer side ofprojection portion 1 a with projection portion 1 a being located in thecenter.

FIG. 4 shows a schematic enlarged cross-sectional view along the lineB-B passing through the center of the projection portion shown in FIG.3. As shown in FIG. 4, in the cross-sectional view passing through thecenter of projection portion 1 a in the plan view of the surface ofsubstrate 1, projection portion 1 a is preferably in a shape having atip end portion 1 c. It is noted herein that the shape of projectionportion 1 a having tip end portion 1 c means that an upper surface ofprojection portion 1 a is not in a flat shape in the cross-sectionalview passing through the center of projection portion 1 a in the planview of the surface of substrate 1. In a case where the upper surface ofprojection portion 1 a is flat, first nitride semiconductor underlyinglayer 4 which will be described later may grow not only on recessportion 1 b but also on a flat upper surface of projection portion 1 a.On the other hand, in a case where projection portion 1 a is in a shapehaving tip end portion 1 c, first nitride semiconductor underlying layer4 grows from recess portion 1 b and second nitride semiconductorunderlying layer 5 which successively grows meets above tip end portion1 c of projection portion 1 a. Therefore, it is considered that a regionwhere a crystal defect is caused is limited and the number of defects asa whole can be decreased.

The surface of substrate 1 may be pre-treated before nitridesemiconductor intermediate layer 2 is formed. One example ofpre-treatment of the surface of substrate 1 includes, for example, suchtreatment as treatment for hydrogen-terminating the surface of substrate1 by carrying out RCA cleaning (cleaning in which treatment with adiluted hydrofluoric acid aqueous solution (HF), treatment with ammonia(NH₄OH)+hydrogen peroxide (H₂O₂), treatment with hydrochloric acid(HCl)+hydrogen peroxide (H₂O₂), and cleaning with ultrapure water aresuccessively carried out). Thus, nitride semiconductor intermediatelayer 2 having good crystallinity tends to be stacked on the surface ofsubstrate 1 with good reproducibility.

Another example of pre-treatment of the surface of substrate 1 includessuch treatment that the surface of substrate 1 is exposed to plasma of anitrogen gas. Thus, such foreign matters as an organic substance or anoxide which has adhered to the surface of substrate 1 tend to be removedand a state of the surface of substrate 1 tends to be conditioned. Inparticular, in a case where substrate 1 is a sapphire substrate, byexposing the surface of substrate 1 to plasma of a nitrogen gas, thesurface of substrate 1 is nitrided and nitride semiconductorintermediate layer 2 stacked on the surface of substrate 1 tends to beformed uniformly in the plane.

Then, as shown in a schematic cross-sectional view in FIG. 5, nitridesemiconductor intermediate layer 2 is formed on the surface of substrate1. Here, nitride semiconductor intermediate layer 2 can be formed, forexample, with reactive sputtering in which an Al target is sputtered ina mixed atmosphere of N₂ and Ar.

For example, a layer composed of a semiconductor nitride expressed witha formula Al_(x0)Ga_(y0)N (0≦x≦1, 0≦y0≦1 x0+y0≠0) can be stacked asnitride semiconductor intermediate layer 2. Among others, a layercomposed of a semiconductor nitride expressed with a formula AlN(aluminum nitride) or Al_(x1)Ga_(1-x1)N (0.5<x1≦1) (aluminum galliumnitride) is preferably stacked as nitride semiconductor intermediatelayer 2. In this case, nitride semiconductor intermediate layer 2 havinggood crystallinity and formed of an aggregate of column crystals uniformin crystal grain extending in a direction of the normal of the surfaceof substrate 1 tends to be obtained. Nitride semiconductor intermediatelayer 2 may contain a trace amount of oxygen.

Nitride semiconductor intermediate layer 2 has a thickness preferablynot smaller than 5 nm and not greater than 100 nm. When nitridesemiconductor intermediate layer 2 has a thickness not smaller than 5nm, nitride semiconductor intermediate layer 2 tends to sufficientlyachieve a function as a buffer layer. When nitride semiconductorintermediate layer 2 has a thickness not greater than 100 nm, a functionas a buffer layer tends to improve and a time period for forming nitridesemiconductor intermediate layer 2 tends to be shortened. Nitridesemiconductor intermediate layer 2 has a thickness more preferably notsmaller than 10 nm and not greater than 50 nm. In this case, a functionof nitride semiconductor intermediate layer 2 as a buffer layer tends tobe achieved uniformly in the plane. By way of example of nitridesemiconductor intermediate layer 2, an AlN film containing a traceamount of oxygen can be formed to a thickness of approximately 25 nm.

A temperature of substrate 1 during formation of nitride semiconductorintermediate layer 2 is preferably not lower than 300° C. and not higherthan 1000° C. When a temperature of substrate 1 during formation ofnitride semiconductor intermediate layer 2 is not lower than 300° C.,nitride semiconductor intermediate layer 2 tends to cover the entiresurface of substrate 1. When a temperature of substrate 1 duringstacking of nitride semiconductor intermediate layer 2 is not higherthan 1000° C., migration of a source material at the surface ofsubstrate 1 is not excessively active, and nitride semiconductorintermediate layer 2 made of an aggregate of column crystals tends to beformed and a function of nitride semiconductor intermediate layer 2 as abuffer layer tends to improve.

Then, as shown in a schematic cross-sectional view in FIG. 6, firstnitride semiconductor underlying layer 4 is formed on the surface ofnitride semiconductor intermediate layer 2, and as shown in a schematiccross-sectional view in FIG. 7, second nitride semiconductor underlyinglayer 5 is formed on the surface of first nitride semiconductorunderlying layer 4.

Here, first nitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 can successively be formed on thesurface of nitride semiconductor intermediate layer 2, for example, withMOCVD (Metal Organic Chemical Vapor Deposition). First nitridesemiconductor underlying layer 4 is grown in a facet growth mode inwhich first oblique facet plane 4 r is formed, and second nitridesemiconductor underlying layer 5 is grown in an embedment growth mode inwhich first oblique facet plane 4 r is buried and flat upper surface 5 ais formed. Thus, second nitride semiconductor underlying layer 5 havingfew crystal defects, high crystallinity, and flat upper surface 5 a canbe formed. It is noted that a reference character 4 c shown in FIG. 6refers to an upper surface of first nitride semiconductor underlyinglayer 4.

FIG. 8 shows a schematic enlarged plan view of one example of thesurface of first nitride semiconductor underlying layer 4 shown in FIG.6. As shown in FIG. 8, first nitride semiconductor underlying layer 4has 6 first oblique facet planes 4 r surrounding projection portion 1 aon the outer side of projection portion 1 a. In the plan view shown inFIG. 8, two first oblique facet planes 4 r appear in the direction ofthe a (sub) axis and two first oblique facet planes 4 r appear in eachof the direction inclined by an angle of 60° with respect to thedirection of the a (sub) axis and the direction inclined by an angle of−60° with respect to the direction of the a (sub) axis (both of whichare the u direction) (this case being referred to as a case 1-1). Inaddition, first oblique facet plane 4 r which appears in a cross-sectionalong the line B-B in FIG. 8 is a plane which similarly appears also ina direction of depth of a cross-section in a range where first obliquefacet planes 4 r are present.

Furthermore, one first oblique facet plane 4 r surrounding projectionportion 1 a and another first oblique facet plane 4 r surroundingprojection portion 1 a are coupled to each other at upper surface 4 c offirst nitride semiconductor underlying layer 4.

First oblique facet plane 4 r of first nitride semiconductor underlyinglayer 4 is inclined downward from upper surface 4 c of first nitridesemiconductor underlying layer 4 toward projection 1 a of substrate 1.Here, among 6 first oblique facet planes 4 r, in the plan view of thesurface of first nitride semiconductor underlying layer 4, two firstoblique facet planes 4 r which appear in the direction of the a (sub)axis are inclined obliquely upward with respect to the direction of thea (sub) axis (<11-20> direction) and the facet plane extends in thedirection of inclination. In addition, similarly, in the plan view ofthe surface of first nitride semiconductor underlying layer 4, two firstoblique facet planes 4 r which appear in each of the direction inclinedby an angle of +60° with respect to the direction of the a (sub) axisand the direction inclined by an angle of −60° with respect to thedirection of the a (sub) axis are also inclined obliquely upward withrespect to the direction inclined by an angle of +60° with respect tothe direction of the a (sub) axis and the direction inclined by an angleof −60° with respect to the direction of the a (sub) axis, and the facetplane extends in the direction of inclination.

In addition, first oblique facet planes 4 r of first nitridesemiconductor underlying layer 4 serve as 6 facet planes surroundingprojection portion 1 a on the outer side of projection portion 1 a withprojection portion 1 a being located in the center, on nitridesemiconductor intermediate layer 2.

Moreover, in the plan view of the surface of first nitride semiconductorunderlying layer 4, substantially no facet plane other than firstoblique facet planes 4 r which appear in the direction of the a (sub)axis and in the u directions preferably appears. More specifically, aratio of area of first oblique facet planes 4 r expressed with thefollowing expression (I) is preferably not lower than 80% and morepreferably not lower than 90%. When a ratio of area of first obliquefacet planes 4 r is not lower than 80% and in particular not lower than90%, occurrence of breakage and crack of a wafer tends to be suppressedduring growth of a nitride semiconductor layer stacked on upper surface5 a of second nitride semiconductor underlying layer 5 and in subsequentprocesses. Furthermore, crystallinity of a nitride semiconductor layerexpressed with a half width of an X-ray rocking curve or the like alsotends to improve. Additionally, defect density which can be evaluatedbased on a cathode luminescence (CL) method, etch pit density (EPD), orthe like also tends to lower. Specifically, a half width (arcsec) of anX-ray rocking curve at a (004) plane of a GaN underlying layer was 30 to40 arcsec. Further, dark spot density obtained with the CL method wasnot higher than 2×10⁸ cm⁻³.

100×(an area of first oblique facet planes 4r occupying the surface offirst nitride semiconductor underlying layer 4 in the plan view of thesurface of first nitride semiconductor underlying layer 4)/(an area of aregion other than upper surfaces 4c and first oblique facet planes 4roccupying the surface of first nitride semiconductor underlying layer 4in the plan view of the surface of first nitride semiconductorunderlying layer 4).  (I)

As first nitride semiconductor underlying layer 4 grows and becomesthicker, first oblique facet planes 4 r develop, and hence a ratio ofarea of upper surfaces 4 c occupied in the total area of the surface offirst nitride semiconductor underlying layer 4 lowers. The ratio of areaof upper surfaces 4 c occupied in the total area of the surface of firstnitride semiconductor underlying layer 4 is preferably not higher than20% and further preferably not higher than 10%. When the ratio of areaof upper surfaces 4 c above is not higher than 20% and in particular nothigher than 10%, occurrence of breakage and crack of a wafer tends to besuppressed during growth of a nitride semiconductor layer stacked onupper surface 5 a of second nitride semiconductor underlying layer 5 andin subsequent processes. In addition, crystallinity of a nitridesemiconductor layer expressed with a half width of an X-ray rockingcurve or the like can also improve. Additionally, defect density whichcan be evaluated with the CL method, EPD, or the like also tends tolower. It is noted that it is not necessary to continue the facet growthmode until upper surface 4 c of first nitride semiconductor underlyinglayer 4 completely disappears.

The facet growth mode for first nitride semiconductor underlying layer 4where first oblique facet plane 4 r as described above appears can berealized by satisfying at least one condition selected from the groupconsisting of

(i-1) setting a growth temperature during growth of first nitridesemiconductor underlying layer 4 to be lower than a growth temperatureduring growth of second nitride semiconductor underlying layer 5,

(ii-1) setting a pressure during growth of first nitride semiconductorunderlying layer 4 to be higher than a pressure during growth of secondnitride semiconductor underlying layer 5, and

(iii-1) setting a V/III ratio of a gas (a molar ratio of a group Velement with respect to a group III element in a supplied gas) suppliedduring growth of first nitride semiconductor underlying layer 4 to behigher than a V/III ratio of a gas supplied during growth of secondnitride semiconductor underlying layer 5.

Specific conditions of (i-1), (ii-1), and (iii-1) above are shown, forexample, as follows:

(i-1) A temperature of substrate 1 during growth of second nitridesemiconductor underlying layer 5 is set to 1080° C. as compared with atemperature of 1000° C. of substrate 1 during growth of first nitridesemiconductor underlying layer 4;

(ii-1) A pressure of an atmosphere during growth of second nitridesemiconductor underlying layer 5 is set to 17.3 kPa as compared with apressure of 66.6 kPa of an atmosphere during growth of first nitridesemiconductor underlying layer 4; and

(iii-1) A V/III ratio of a gas supplied during growth of second nitridesemiconductor underlying layer 5 is set to 676 as compared with a V/IIIratio of 1165 of a gas supplied during growth of first nitridesemiconductor underlying layer 4.

By satisfying at least one condition selected from the group consistingof (i-1), (ii-1), and (iii-1) above, yield in an electrostatic dischargetest (an ESD test) of a large number of semiconductor light emittingelements formed in a wafer can be not lower than 80%. It is noted thatthe ESD test is conducted under an HBM (human body model) condition inwhich a reverse voltage is set to 1 kV.

It is noted that a thickness of each of first nitride semiconductorunderlying layer 4 and second nitride semiconductor underlying layer 5is preferably not less than 0.7 time and not more than 4 times as greatas an interval between adjacent projection portions 1 a in the plan viewof the surface of substrate 1 above. When a thickness of each of firstnitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 is not less than 0.7 time as great asan interval between adjacent projection portions la, projection portion1 a tends to be buried, and when the thickness is not more than 4 times,first nitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 each tend to be a film having fewcrystal defects and hence having good crystallinity.

In addition, a thickness of first nitride semiconductor underlying layer4 is preferably not less than 0.5 time and not more than 2 times asgreat as an interval between adjacent projection portions 1 a in theplan view of the surface of substrate 1 above. When a thickness of firstnitride semiconductor underlying layer 4 is not less than 0.5 time andnot more than 2 times as great as an interval between adjacentprojection portions 1 a, first nitride semiconductor underlying layer 4and second nitride semiconductor underlying layer 5 each tend to be afilm having few crystal defects and hence having good crystallinity.

On the other hand, a thickness of second nitride semiconductorunderlying layer 5 is preferably not less than 1 time and not more than4 times as great as an interval between adjacent projection portions 1 ain the plan view of the surface of substrate 1 above. When a thicknessof second nitride semiconductor underlying layer 5 is not less than 1time as great as an interval between adjacent projection portions 1 a,second nitride semiconductor underlying layer 5 tends to bury projectionportion 1 a and upper surface 5 a of second nitride semiconductorunderlying layer 5 tends to be flat. When a thickness of second nitridesemiconductor underlying layer 5 is more than 4 times as great as aninterval between adjacent projection portions 1 a, upper surface 5 a ofsecond nitride semiconductor underlying layer 5 has already become flatand hence only a time period of growth of second nitride semiconductorunderlying layer 5 simply tends to be longer.

FIG. 9 shows a schematic enlarged plan view of another example of thesurface of first nitride semiconductor underlying layer 4 shown in FIG.6. FIG. 9 shows positional relation between first oblique facet plane 4r and upper surface 4 c of nitride semiconductor underlying layer 4 in acase where projection portions 1 a at the surface of substrate 1 arearranged in a direction inclined by +30° with respect to the directionof the a (sub) axis and in a direction inclined by −30° with respect tothe direction of the a (sub) axis (a case 1-2).

In a case of growing first nitride semiconductor underlying layer 4 in afacet mode in which 6 first oblique facet planes 4 r are formed, firstoblique facet planes 4 r and upper surface 4 c of nitride semiconductorunderlying layer 4 are more likely to be affected by arrangement ofprojection portions 1 a.

In case 1-2, in the plan view of the surface of first nitridesemiconductor underlying layer 4, upper surface 4 c of first nitridesemiconductor underlying layer 4 is in such a shape as continuingtriangles, and second nitride semiconductor underlying layer 5 is formedon upper surface 4 c after switching to the embedment growth mode, whichis a mode of growth of second nitride semiconductor underlying layer 5,has been made. Since upper surface 4 c may have taken over crystaldefects from an underlying layer thereof, growth on arrangement ofprojection portions 1 a in case 1-2 tends to slightly be greater in thenumber of crystal defects in a nitride semiconductor film formedthereon.

In case 1-2, yield in an ESD test of a large number of semiconductorlight emitting elements formed in a wafer was approximately 20%. It isnoted that the ESD test is conducted under an HBM condition in which areverse voltage is set to 1 kV.

FIG. 10 shows a schematic enlarged plan view of another example of thesurface of first nitride semiconductor underlying layer 4 shown in FIG.6. FIG. 10 shows the surface of first nitride semiconductor underlyinglayer 4 in a case (a case 1-3) where first nitride semiconductorunderlying layer 4 is grown in a facet growth mode different from case1-1, although arrangement of projection portions 1 a at substrate 1 isthe same as in case 1-1 above.

A condition for growth of first nitride semiconductor underlying layer 4in case 1-3 is, for example, such that a temperature of substrate 1during growth of first nitride semiconductor underlying layer 4 whichwas set to 1000° C. is raised to 1080° C. which is the same as atemperature of substrate 1 during growth of second nitride semiconductorunderlying layer 5.

In first nitride semiconductor underlying layer 4 in case 1-3, in theplan view of the surface of first nitride semiconductor underlying layer4 shown in FIG. 10, 12 facet planes consisting of 6 first oblique facetplanes 4 n which appear in a direction inclined by +30° with respect tothe direction of the a (sub) axis, in a direction inclined by −30° withrespect to the direction of the a (sub) axis, and in a direction of them (sub) axis, in addition to 6 first oblique facet planes 4 r whichappear in the direction of the a (sub) axis and the u directions, areformed.

In case 1-3, yield in an ESD test of a large number of semiconductorlight emitting elements formed in a wafer was approximately 70%. It isnoted that the ESD test is conducted under an HBM condition in which areverse voltage is set to 1 kV. It is noted that, in case 1-3, duringgrowth with MOCVD and in subsequent processes, due to fluctuation ofwarpage of the entire wafer caused by temperature change, 3 of 4 wafersbroke and measurement could not be conducted. It was thus found that, ina case where first oblique facet plane 4 r and first oblique facet plane4 n both appear, breakage of a wafer is likely to take place. Ahypothesis of this phenomenon is as follows. A crystal orientation of afilm grown on first oblique facet plane 4 r and a crystal orientation ofa plane grown on first oblique facet plane 4 n are slightly displacedfrom each other, which causes a line defect at an interfacetherebetween, and the film breaks along a line corresponding to a seriesof such lines. Consequently, strain involved with difference in thermalexpansion between the film and substrate 1 may concentrate in thatportion and a wafer may break.

FIG. 11 shows a schematic enlarged plan view of another example of thesurface of first nitride semiconductor underlying layer 4 shown in FIG.6. FIG. 11 shows the surface of nitride semiconductor underlying layer 4in a case (a case 1-4) where arrangement of projection portions 1 a isthe same as that in case 1-2 and first nitride semiconductor underlyinglayer 4 is grown under growth conditions the same as those in case 1-3.

In first nitride semiconductor underlying layer 4 in case 1-4, in theplan view of the surface of first nitride semiconductor underlying layer4 shown in FIG. 11, 12 facet planes consisting of 6 first oblique facetplanes 4 n which appear in directions inclined by ±30° with respect tothe direction of the a (sub) axis and in the direction of the m (sub)axis, in addition to 6 first oblique facet planes 4 r which appear inthe direction of the a (sub) axis and the u directions, are formed.

In case 1-4, yield in an ESD test of a large number of semiconductorlight emitting elements formed in a wafer was approximately 30%. It isnoted that the ESD test is conducted under an HBM condition in which areverse voltage is set to 1 kV.

It is noted that, as in case 1-3, in case 1-4 as well, during growthwith MOCVD and in subsequent processes, 3 of 4 wafers broke.

From the foregoing results, the following matters (a-1) to (c-1) arederived:

(a-1) The facet growth mode in which first oblique facet plane 4 r offirst nitride semiconductor underlying layer 4 dominantly appears andfirst oblique facet plane 4 n is less likely to appear is suitablebecause a wafer is less likely to break and high yield is obtained in anESD test;

(b-1) It is suitable to decrease an area of upper surfaces 4 c of firstnitride semiconductor underlying layer 4 in the plan view of the surfaceof first nitride semiconductor underlying layer 4 because high yield isobtained in an ESD test; and

(c-1) A large number of line defects extending upward from a lowersurface of first nitride semiconductor underlying layer 4 are consideredto be present at upper surface 4 c of first nitride semiconductorunderlying layer 4, and those defects are considered to be taken overalso by second nitride semiconductor underlying layer 5 grown on facetplane 4 c.

It is noted that, for example, a layer composed of a group III nitridesemiconductor expressed with a formula Al_(x2)Ga_(y2)In_(z2)N (0≦x2≦1,0≦y2≦1, 0≦z2≦1, x2+y2+z2≠0) can be grown as first nitride semiconductorunderlying layer 4. In addition, for example, a layer composed of agroup III nitride semiconductor expressed with a formulaAl_(x3)Ga_(y3)In_(z3)N (0≦x3≦1, 0≦y3≦1, 0≦z3≦1, x3+y3+z3≠0) can be grownas second nitride semiconductor underlying layer 5.

In order not to take over such a crystal defect as dislocation innitride semiconductor intermediate layer 2 made of an aggregate ofcolumn crystals, a nitride semiconductor layer containing Ga as a groupIII element is preferably employed for first nitride semiconductorunderlying layer 4 and second nitride semiconductor underlying layer 5.

In order not to take over dislocation in nitride semiconductorintermediate layer 2, dislocation loop should be formed around aninterface with nitride semiconductor intermediate layer 2. In a casewhere first nitride semiconductor underlying layer 4 is composed of agroup III nitride semiconductor containing Ga, dislocation loop islikely to be formed. Then, by employing first nitride semiconductorunderlying layer 4 composed of a group III nitride semiconductorcontaining Ga and second nitride semiconductor underlying layer 5containing Ga, dislocation is confined as a loop around the interfacewith nitride semiconductor intermediate layer 2, so that taking over ofdislocation from nitride semiconductor intermediate layer 2 into firstnitride semiconductor underlying layer 4 tends to be suppressed.

For example, in a case where first nitride semiconductor underlyinglayer 4 is composed of a group III nitride semiconductor expressed witha formula Al_(x2)Ga_(y2)N (0x2<1, 0<y2<1) and second nitridesemiconductor underlying layer 5 is composed of a group III nitridesemiconductor expressed with a formula Al_(x0)Ga_(y3)N (0≦x3<1, 0<y3<1)and in particular in a case where first nitride semiconductor underlyinglayer 4 and second nitride semiconductor underlying layer 5 are eachcomposed of GaN, dislocation can be confined as a loop around theinterface with nitride semiconductor intermediate layer 2, so that firstnitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 having low dislocation density and goodcrystallinity tend to be obtained.

In addition, the surface of nitride semiconductor intermediate layer 2immediately before first nitride semiconductor underlying layer 4 isformed may be subjected to heat treatment. Through this heat treatment,a cleaner surface and improvement in crystallinity of nitridesemiconductor intermediate layer 2 tend to be achieved. This heattreatment can be carried out, for example, in an MOCVD apparatus inwhich MOCVD is employed, and for example, a hydrogen gas, a nitrogengas, or the like can be employed as an atmospheric gas during heattreatment.

Moreover, in order to prevent decomposition of nitride semiconductorintermediate layer 2 during heat treatment above, an ammonia gas may bemixed with the atmospheric gas during heat treatment. Furthermore, heattreatment above can be carried out, for example, at a temperature notlower than 900° C. and not higher than 1250° C., for example, for a timeperiod not shorter than 1 minute and not longer than 60 minutes.

First nitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 may be doped, for example, with ann-type dopant in a range not lower than 1×10¹⁷ cm⁻³ and not higher than1×10¹⁹ cm⁻³. From a point of view of maintaining good crystallinity,however, first nitride semiconductor underlying layer 4 and secondnitride semiconductor underlying layer 5 are preferably undoped.

For example, at least one or the like selected from the group consistingof silicon, germanium, and tin can be employed as an n-type dopant withwhich first nitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 are doped, and among these, use ofsilicon is preferred. In a case of using silicon as an n-type dopant,silane or disilane is preferably used as an n-type doping gas.

A temperature of substrate 1 during growth of each of first nitridesemiconductor underlying layer 4 and second nitride semiconductorunderlying layer 5 is preferably not lower than 800° C. and not higherthan 1250° C. and more preferably not lower than 900° C. and not higherthan 1150° C. When a temperature of substrate 1 during growth of each offirst nitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 is not lower than 800° C. and nothigher than 1250° C. and in particular not lower than 900° C. and nothigher than 1150° C., first nitride semiconductor underlying layer 4 andsecond nitride semiconductor underlying layer 5 having few crystaldefects and excellent crystallinity tend to be grown.

Then, as shown in a schematic cross-sectional view in FIG. 12, forexample, with MOCVD, n-type nitride semiconductor contact layer 7 isformed on the surface of second nitride semiconductor underlying layer5.

For example, a layer obtained by doping with an n-type dopant, a layercomposed of a group III nitride semiconductor expressed with a formulaAl_(x-4)Ga_(y-4)In_(z4)N (0≦x4≦1, 0≦y4≦1, 0≦z4≦1, x4+y4−z4≠0) or thelike, can be formed as n-type nitride semiconductor contact layer 7.

Among others, a nitride semiconductor layer obtained by doping withsilicon as an n-type dopant, a group III nitride semiconductor expressedwith a formula Al_(x4)Ga_(1-x4)N (0≦x4≦1, preferably 0≦x4≦0.5, morepreferably 0≦x4≦0.1), is preferred as n-type nitride semiconductorcontact layer 7, because In which is readily volatilized is not handledand a growth temperature can be raised.

Concentration of doping of n-type nitride semiconductor contact layer 7with an n-type dopant is preferably not lower than 5×10¹⁷ cm⁻³ and nothigher than 5×10¹⁹ cm⁻³. In this case, good ohmic contact tends to bemaintained between n-type nitride semiconductor contact layer 7 andn-side electrode 20, occurrence of a crack in n-type nitridesemiconductor contact layer 7 tends to be suppressed, and goodcrystallinity of n-type nitride semiconductor contact layer 7 tends tobe maintained.

A total thickness of first nitride semiconductor underlying layer 4,second nitride semiconductor underlying layer 5, and n-type nitridesemiconductor contact layer 7 is preferably not smaller than 4 μm andnot greater than 20 μm, more preferably not smaller than 4 μm and notgreater than 15 μm, and further preferably not smaller than 6 μm and notgreater than 15 μm. When a total thickness of first nitridesemiconductor underlying layer 4, second nitride semiconductorunderlying layer 5, and n-type nitride semiconductor contact layer 7 issmaller than 4 μm, crystallinity of these layers may become poorer or apit may be caused in a surface of these layers. On the other hand, whena total thickness of first nitride semiconductor underlying layer 4,second nitride semiconductor underlying layer 5, and n-type nitridesemiconductor contact layer 7 exceeds 15 μm, warpage of substrate 1 maybecome great and lowering in yield of an element may be caused. When atotal thickness of first nitride semiconductor underlying layer 4,second nitride semiconductor underlying layer 5, and n-type nitridesemiconductor contact layer 7 is not smaller than 4 μm and not greaterthan 15 μm and in particular not smaller than 6 μm and not greater than15 μm, crystallinity of these layers tends to be good, warpage ofsubstrate 1 tends to be great, and lowering in yield of an element tendsto effectively be prevented. It is noted that an upper limit of athickness of n-type nitride semiconductor contact layer 7 of the totalthickness of these layers is not particularly limited.

Then, as shown in a schematic cross-sectional view in FIG. 13, forexample, with MOCVD, n-type nitride semiconductor clad layer 9 is formedon the surface of n-type nitride semiconductor contact layer 7.

For example, a layer obtained by doping with an n-type dopant, a layercomposed of a group III nitride semiconductor expressed with a formulaAl_(x5)Ga_(y5)In_(z5)N (0≦x5≦1, 0≦y5≦1, 0≦z5≦1, x5+y5+z5≠0) or the like,can be formed as n-type nitride semiconductor clad layer 9. N-typenitride semiconductor clad layer 9 may have a structure obtained byhetero-junction of a plurality of nitride semiconductor layers composedof a group III nitride semiconductor or a superlattice structure.

Though a thickness of n-type nitride semiconductor clad layer 9 is notparticularly limited, a thickness not smaller than 0.005 μm and notgreater than 0.5 μm is preferred and a thickness not smaller than 0.005μm and not greater than 0.1 μm is more preferred.

Concentration of doping of n-type nitride semiconductor clad layer 9with an n-type dopant is preferably not lower than 1×10¹⁷ cm⁻³ and nothigher than 1×10²⁰ cm⁻³ and more preferably not lower than 1×10¹⁸ cm⁻³and not higher than 1×10¹⁹ cm³. In this case, good crystallinity ofn-type nitride semiconductor clad layer 9 tends to be maintained and anoperation voltage of an element tends to be lowered.

Then, as shown in a schematic cross-sectional view in FIG. 14, forexample, with MOCVD, nitride semiconductor active layer 11 is formed onthe surface of n-type nitride semiconductor clad layer 9.

When nitride semiconductor active layer 11 has, for example, a singlequantum well (SQW) structure, for example, a layer having as a quantumwell layer, a layer composed of a group III nitride semiconductorexpressed with a formula Ga_(1-z6)In_(z6)N (0<z6<0.4), can be employedas nitride semiconductor active layer 11.

Though a thickness of nitride semiconductor active layer 11 is notparticularly limited, a thickness not smaller than 1 nm and not greaterthan 10 nm is preferred and a thickness not smaller than 1 nm and notgreater than 6 nm is more preferred. When a thickness of nitridesemiconductor active layer 11 is not smaller than 1 nm and not greaterthan 10 nm and in particular not smaller than 1 nm and not greater than6 nm, emission output of nitride semiconductor light emitting diodeelement 100 tends to improve.

When nitride semiconductor active layer 11 has a single quantum well(SQW) structure, for example, having as a quantum well layer, a layercomposed of a group III nitride semiconductor expressed with the formulaGa_(1-z6)In_(z6)N (0<z6<0.4), In composition or a thickness of nitridesemiconductor active layer 11 can be controlled such that an emissionwavelength of nitride semiconductor light emitting diode element 100attains to a desired emission wavelength.

When a temperature of substrate 1 during formation of nitridesemiconductor active layer 11 is low, however, crystallinity may becomepoor. On the other hand, when a temperature of substrate 1 duringformation of nitride semiconductor active layer 11 is high, sublimationof InN may become noticeable, efficiency in taking In into a solid phasemay be lowered, and In composition may fluctuate. Therefore, atemperature of substrate 1 during formation of nitride semiconductoractive layer 11 formed from a single quantum well (SQW) structure havingas a well layer, a layer composed of a group III nitride semiconductorexpressed with the formula Ga_(1-z6)In_(z6)N (0<z6<0.4), is preferablynot lower than 700° C. and not higher than 900° C. and more preferablynot lower than 750° C. and not higher than 850° C.

Furthermore, for example, a layer having a multiple quantum well (MQW)structure formed by alternately stacking a quantum well layer composedof a group III nitride semiconductor expressed with the formulaGa_(1-z6)In_(z6)N (0<z6<0.4) and a quantum barrier layer composed of agroup III nitride semiconductor expressed with a formulaAl_(x0)Ga_(y7)In_(z7)N (0≦x7≦1, 0≦y7≦1, 0≦z7≦1, x7+y7+z7≠0) greater inband gap than the quantum well layer can also be employed as nitridesemiconductor active layer 11. It is noted that the quantum well layerand/or the quantum barrier layer above may be doped with an n-type orp-type dopant.

Then, as shown in a schematic cross-sectional view in FIG. 15, forexample, with MOCVD, p-type nitride semiconductor clad layer 13 isformed on the surface of nitride semiconductor active layer 11.

For example, a layer obtained by doping with a p-type dopant, a groupIII nitride semiconductor expressed with a formulaAl_(x8)Ga_(y8)In_(z8)N (0≦x8≦1, 0≦y8≦1, 0≦z8≦1, x8+y8+z8≠0) or the like,can be stacked as p-type nitride semiconductor clad layer 13. Amongothers, a layer obtained by doping with a p-type dopant, a group IIInitride semiconductor expressed with a formula Al_(x8)Ga_(1-x8) N(0<x8≦0.4, preferably 0.1≦x8≦0.3), is preferably stacked as p-typenitride semiconductor clad layer 13. It is noted that, for example,magnesium or the like can be employed for a p-type dopant.

From a point of view of optical confinement in nitride semiconductoractive layer 11, p-type nitride semiconductor clad layer 13 ispreferably greater in band gap than nitride semiconductor active layer11.

Though a thickness of p-type nitride semiconductor clad layer 13 is notparticularly limited, a thickness not smaller than 0.01 μm and notgreater than 0.4 μm is preferred and a thickness not smaller than 0.02μm and not greater than 0.1 μm is more preferred.

Concentration of doping of p-type nitride semiconductor clad layer 13with a p-type dopant is preferably not lower than 1×10¹⁸ cm⁻³ and nothigher than 1×10²¹ cm⁻³ and more preferably not lower than 1×10¹⁹ cm⁻³and not higher than 1×10²¹ cm⁻³. When concentration of doping of p-typenitride semiconductor clad layer 13 with a p-type dopant is not lowerthan 1×10¹⁸ cm⁻³ and not higher than 1×10²¹ cm³ and in particular notlower than 1×10¹⁹ cm⁻³ and not higher than 1×10²⁰ cm⁻³, p-type nitridesemiconductor clad layer 13 having good crystallinity tends to beobtained.

Then, as shown in a schematic cross-sectional view in FIG. 16, forexample, with MOCVD, p-type nitride semiconductor contact layer 15 isformed on the surface of p-type nitride semiconductor clad layer 13.

For example, a layer obtained by doping with a p-type dopant, a groupIII nitride semiconductor expressed with a formulaAl_(x9)Ga_(y9)In_(z9)N (0≦x9≦1, 0≦y9≦1, 0≦z9≦1, x9+y9+z9≠0) or the like,can be stacked as p-type nitride semiconductor contact layer 15. Amongothers, a layer obtained by doping a GaN layer with a p-type dopant ispreferably employed as p-type nitride semiconductor contact layer 15. Inthis case, good crystallinity of p-type nitride semiconductor contactlayer 15 tends to be maintained and good ohmic contact with lighttransmitting electrode layer 19 tends to be obtained.

Concentration of doping of p-type nitride semiconductor contact layer 15with a p-type dopant is preferably not lower than 1×10¹⁸ cm⁻³ and nothigher than 1×10²¹ cm⁻³ and more preferably not lower than 5×10¹⁹ cm⁻³and not higher than 5×10²⁰ cm⁻³. When concentration of doping of p-typenitride semiconductor contact layer 15 with a p-type dopant is not lowerthan 1×10¹⁸ cm⁻³ and not higher than 1×10²¹ cm⁻³ and in particular notlower than 5×10¹⁹ cm⁻³ and not higher than 5×10²⁰ cm⁻³, good ohmiccontact with light transmitting electrode layer 19 tends to bemaintained, occurrence of a crack in p-type nitride semiconductorcontact layer 15 tends to be suppressed, and good crystallinity ofp-type nitride semiconductor contact layer 15 tends to be maintained.

Though a thickness of p-type nitride semiconductor contact layer 15 isnot particularly limited, a thickness not smaller than 0.01 μm and notgreater than 0.5 μm is preferred and a thickness not smaller than 0.05μm and not greater than 0.2 μm is more preferred. When a thickness ofp-type nitride semiconductor contact layer 15 is not smaller than 0.01μm and not greater than 0.5 μm and in particular not smaller than 0.05μm and not greater than 0.2 μm, emission output of nitride semiconductorlight emitting diode element 100 tends to improve.

It is noted that, when each of n-type nitride semiconductor contactlayer 7, n-type nitride semiconductor clad layer 9, nitridesemiconductor active layer 11, p-type nitride semiconductor clad layer13, and p-type nitride semiconductor contact layer 15 is composed of agroup III nitride semiconductor, these layers can each be stacked, forexample, with MOCVD using a gas below.

Namely, for example, at least one group-III-element organic metal sourcematerial gas selected from the group consisting of trimethylgallium(TMG), trimethylaluminum (TMA), and trimethylindium (TMI), and anitrogen source material gas such as ammonia are supplied into areaction furnace of an MOCVD apparatus, to thereby achieve thermaldecomposition and reaction thereof. Thus, the layers above can each bestacked.

When doping with silicon representing an n-type dopant is carried out,doping with silicon can be achieved, for example, by adding silane(SiH₄) or disilane (Si₂H₆) as a doping gas to the source material gasabove and supplying the resultant gas into the reaction furnace of theMOCVD apparatus.

When doping with magnesium representing a p-type dopant is carried out,doping with magnesium can be achieved, for example, by addingbis(cyclopentadienyl) magnesium (CP₂Mg) as a doping gas to the sourcematerial gas above and supplying the resultant gas into the reactionfurnace of the MOCVD apparatus.

Then, as shown in a schematic cross-sectional view in FIG. 17, afterlight transmitting electrode layer 19 composed, for example, of ITO(Indium Tin Oxide) is formed on the surface of p-type nitridesemiconductor contact layer 15, p-side electrode 21 is formed on thesurface of light transmitting electrode layer 19. For example, a stackfilm of a nickel layer, an aluminum layer, a titanium layer, and a goldlayer can be formed as p-side electrode 21.

Then, as shown in a schematic cross-sectional view in FIG. 18, a part ofthe surface of n-type nitride semiconductor contact layer 7 is exposedby etching away a part of a stack structure after p-side electrode 21 isformed.

Then, as shown in a schematic cross-sectional view in FIG. 19, n-sideelectrode 20 is formed on the exposed surface of n-type nitridesemiconductor contact layer 7. For example, a stack film of a nickellayer, an aluminum layer, a titanium layer, and a gold layer can beformed as n-side electrode 20.

Thereafter, insulating protection film 23 composed of SiO₂ or the likeis formed on the entire surface of the stack structure after n-sideelectrode 20 is formed, an opening is provided in insulating protectionfilm 23 so as to expose p-side electrode 21 and n-side electrode 20, anda wafer on which a plurality of nitride semiconductor light emittingdiode elements 100 are formed is divided into individual elements, sothat nitride semiconductor light emitting diode element 100 according toEmbodiment 1-1 can be fabricated.

Here, division of a wafer can be achieved, for example, by grinding andpolishing a back surface of the wafer having the structure above formedon substrate 1 to a mirror surface and thereafter dividing the waferinto rectangular chips each having a dimension of 280 μm×550 μm.

In nitride semiconductor light emitting diode element 100 according toEmbodiment 1-1 fabricated as above, first nitride semiconductorunderlying layer 4, second nitride semiconductor underlying layer 5,n-type nitride semiconductor contact layer 7, n-type nitridesemiconductor clad layer 9, nitride semiconductor active layer 11,p-type nitride semiconductor clad layer 13, and p-type nitridesemiconductor contact layer 15 are stacked in this order on the surfaceof nitride semiconductor intermediate layer 2 having good crystallinityand made of an aggregate of column crystals uniform in crystal grainextending in a direction of the normal (a perpendicular direction) ofthe surface of substrate 1.

Therefore, n-type nitride semiconductor contact layer 7, n-type nitridesemiconductor clad layer 9, nitride semiconductor active layer 11,p-type nitride semiconductor clad layer 13, and p-type nitridesemiconductor contact layer 15 stacked on flat upper surface 5 a ofsecond nitride semiconductor underlying layer 5 having few crystaldefects and high crystallinity are low in dislocation density andexcellent in crystallinity.

Thus, nitride semiconductor light emitting diode element 100 accordingto Embodiment 1-1 formed of such a nitride semiconductor layer havingexcellent crystallinity is an element low in operation voltage and highin emission output.

It is noted that nitride semiconductor light emitting diode element 100fabricated under the conditions in case 1-1 was adopted as a bare chip(not sealed with resin as will be described later) evaluation element,and a current of 30 mA was fed to 10 elements. Then, it was confirmedthat an element low in operation voltage and high in emission output,which achieved light output of 39 mW, an operation voltage of 3.0 V, andan emission wavelength of 455 nm on average, was obtained.

FIG. 20 shows a schematic cross-sectional view of one example of a lightemitting device including nitride semiconductor light emitting diodeelement 100 according to Embodiment 1-1.

Here, a light emitting device 110 has such a construction that nitridesemiconductor light emitting diode element 100 according to Embodiment1-1 is set on a second lead frame 31. Then, p-side electrode 21 ofnitride semiconductor light emitting diode element 100 and a first leadframe 30 are electrically connected to each other through a first wire33, and n-side electrode 20 of nitride semiconductor light emittingdiode element 100 and second lead frame 31 are electrically connected toeach other through a second wire 34. In addition, since nitridesemiconductor light emitting diode element 100 is molded with atransparent molding resin 35, light emitting device 110 is in a shape ofa cannonball.

Since light emitting device 110 having the construction shown in FIG. 20includes nitride semiconductor light emitting diode element 100according to Embodiment 1-1, a light emitting device low in operationvoltage and high in emission output can be achieved.

Embodiment 1-2

Embodiment 1-2 is characterized by being directed to a nitridesemiconductor transistor element which is an electronic device includingthe nitride semiconductor structure according to Embodiment 1-1 (a stackstructure of substrate 1, nitride semiconductor intermediate layer 2,first nitride semiconductor underlying layer 4, and second nitridesemiconductor underlying layer 5).

FIG. 21 shows a schematic cross-sectional view of a nitridesemiconductor transistor element 300 according to Embodiment 1-2.Nitride semiconductor transistor element 300 has a nitride semiconductorstructure constituted of substrate 1 formed of a sapphire substratehaving a c plane as a main surface, in which projection portions 1 a arearranged in three equivalent directions of the a (sub) axis, as well asnitride semiconductor intermediate layer 2 composed of AlN or the like,first nitride semiconductor underlying layer 4 composed of undoped GaNor the like, and second nitride semiconductor underlying layer 5composed of undoped GaN or the like, which are successively stacked onthe surface of substrate 1.

Then, a nitride semiconductor electron transit layer 71 composed ofundoped GaN or the like is stacked on the flat surface of second nitridesemiconductor underlying layer 5 having few crystal defects and goodcrystallinity, and an n-type nitride semiconductor electron supply layer73 composed of n-type AlGaN or the like is stacked on a surface ofnitride semiconductor electron transit layer 71.

A gate electrode 77 is provided on a surface of n-type nitridesemiconductor electron supply layer 73, and a source contact layer 75Sand a drain contact layer 75D composed of n-type GaN or the like areprovided on respective opposing sides of gate electrode 77. In addition,a source electrode 78S is provided on source contact layer 75S, and adrain electrode 78D is provided on drain contact layer 75D.

One example of a method of manufacturing nitride semiconductortransistor element 300 according to Embodiment 1-2 will be describedbelow. Initially, as in Embodiment 1-1, nitride semiconductorintermediate layer 2 composed of AlN is formed with reactive sputteringon the surface of substrate 1 having projection portions 1 a and recessportions 1 b.

Then, first nitride semiconductor underlying layer 4 composed of undopedGaN is grown on the surface of nitride semiconductor intermediate layer2 with MOCVD. Here, first nitride semiconductor underlying layer 4 isgrown under such conditions that two first oblique facet planes 4 rwhich appear in the direction of the a (sub) axis and two first obliquefacet planes 4 r which appear in each of the direction inclined by anangle of +60°with respect to the direction of the a (sub) axis and thedirection inclined by an angle of −60° with respect to the direction ofthe a (sub) axis appear (for example, under the conditions in case 1-1)in the plan view of the surface of first nitride semiconductorunderlying layer 4.

Then, second nitride semiconductor underlying layer 5 composed ofundoped GaN is grown on the surface of first nitride semiconductorunderlying layer 4 with MOCVD. Here, second nitride semiconductorunderlying layer 5 is grown under such conditions that first obliquefacet plane 4 r of first nitride semiconductor underlying layer 4 isburied and substantially flat upper surface 5 a appears.

Then, with MOCVD, nitride semiconductor electron transit layer 71composed of n-type Al_(x)Ga_(1-x)N is stacked on substantially flatupper surface 5 a of second nitride semiconductor underlying layer 5 andn-type nitride semiconductor electron supply layer 73 is stacked on thesurface of nitride semiconductor electron transit layer 71.

Thereafter, as shown in FIG. 21, after source contact layer 75S anddrain contact layer 75D are formed on the surface of n-type nitridesemiconductor electron supply layer 73, source electrode 78S, drainelectrode 78D, and gate electrode 77 are each formed. Nitridesemiconductor transistor element 300 according to Embodiment 1-2 can befabricated as above.

In nitride semiconductor transistor element 300 according to Embodiment1-2 as well, as in Embodiment 1-1, in the plan view of the surface offirst nitride semiconductor underlying layer 4, first nitridesemiconductor underlying layer 4 is grown under such conditions that twofirst oblique facet planes 4 r which appear in the direction of the a(sub) axis and two first oblique facet planes 4 r which appear in eachof the direction inclined by an angle of +60° with respect to thedirection of the a (sub) axis and the direction inclined by an angle of−60° with respect to the direction of the a (sub) axis appear. Thus,since crystal defects in a two-dimensional electron transit region at anuppermost surface of nitride semiconductor electron transit layer 71 aredecreased in particular, electron mobility can be improved.

Therefore, in nitride semiconductor transistor element 300 according toEmbodiment 1-2 as well, each layer stacked on the surface of nitridesemiconductor intermediate layer 2 can be a layer low in dislocationdensity and excellent in crystallinity, and hence an element achievingimproved characteristics such as electron mobility can be obtained.

As above, according to the present embodiment, a shape of first nitridesemiconductor underlying layer 4 and second nitride semiconductorunderlying layer 5 stacked on the surface of substrate 1 havingprojection portions 1 a and recess portions 1 b is controlled. Thus,while occurrence of breakage and crack of a wafer during growth withMOCVD of a nitride semiconductor layer stacked on upper surface 5 a ofsecond nitride semiconductor underlying layer 5 and in subsequentprocesses is suppressed, crystallinity expressed with an X-ray halfwidth or the like of a nitride semiconductor layer can be improved anddefect density expressed with the CL method, EPD, or the like can belowered. Therefore, a nitride semiconductor element achieving improveddevice characteristics represented by emission efficiency, electronmobility, and the like and a nitride semiconductor structure serving asa basis for the nitride semiconductor element can be provided.

Embodiment 2-1

FIG. 22 shows a schematic cross-sectional view of a nitridesemiconductor light emitting diode element according to Embodiment 2-1representing another example of the nitride semiconductor elementaccording to the present invention.

A nitride semiconductor light emitting diode element 200 according toEmbodiment 2-1 is characterized by including a third nitridesemiconductor underlying layer 3 provided in contact with the surface ofnitride semiconductor intermediate layer 2 mainly in recess portion 1 b,first nitride semiconductor underlying layer 4 provided in contact atleast with third nitride semiconductor underlying layer 3, secondnitride semiconductor underlying layer 5 provided in contact at leastwith the surface of first nitride semiconductor underlying layer 4 (andconstituted of a lower layer 5A and an upper layer 5B), and an n-typenitride semiconductor superlattice layer 92 provided on the surface ofn-type nitride semiconductor contact layer 7.

Third nitride semiconductor underlying layer 3 has a third oblique facetplane 3 f provided on recess portion 1 b of substrate 1 and surroundingprojection portion 1 a on the outer side of projection portion 1 a ofsubstrate 1 and a third flat region 3 c coupling third oblique facetplanes 3 f to each other.

In addition, at the surface of third nitride semiconductor underlyinglayer 3, a ratio of area of third oblique facet plane 3 f is lower thana ratio of area of third flat region 3 c.

First nitride semiconductor underlying layer 4 has at least 6 firstoblique facet planes 4 r surrounding projection portion 1 a on the outerside of projection portion 1 a of substrate 1 and has a first flatregion 4 c coupling first oblique facet planes 4 r to each other. Firstoblique facet plane 4 r includes a plane inclined with respect to adirection of an m (layer) axis of a nitride semiconductor layer having ahexagonal structure, and first flat region 4 c is a plane perpendicularto the direction of the m (layer) axis of the nitride semiconductorlayer having the hexagonal structure. It is noted that first nitridesemiconductor underlying layer 4 should only be provided such that atleast a part thereof is in contact with third nitride semiconductorunderlying layer 3.

A lower surface (a lower surface of lower layer 5A) 5L of second nitridesemiconductor underlying layer 5 is in contact with first oblique facetplane 4 r of first nitride semiconductor underlying layer 4, and anupper surface (an upper surface of upper layer 5B) 5U of second nitridesemiconductor underlying layer 5 is flat. In addition, an upper surface(a lower surface of upper layer 5B) 5M of lower layer 5A of secondnitride semiconductor underlying layer 5 is also flat. It is noted thatsecond nitride semiconductor underlying layer 5 should only be providedsuch that at least a part thereof is in contact with the surface offirst nitride semiconductor underlying layer 4.

For example, upper surface 5M of lower layer 5A of second nitridesemiconductor underlying layer 5 and upper surface 5U of second nitridesemiconductor underlying layer 5 each have surface roughness Ra (JIS B0601:2001) not greater than 0.1 μm.

One example of a method of manufacturing nitride semiconductor lightemitting diode element 200 according to Embodiment 2-1 will be describedbelow.

Initially, substrate 1 composed of trigonal corundum or hexagonalcrystal is prepared. For example, a substrate made of sapphire (Al₂O₃)single crystal, AlN single crystal, GaN single crystal, or the like canbe employed as substrate 1 composed of trigonal corundum or hexagonalcrystal.

Though a diameter of substrate 1 is not particularly limited, forexample, it can be 150 mm (approximately 6 inches). Though a substratehaving a relatively small diameter around 50.8 mm (2 inches) hasconventionally generally been employed as substrate 1, a substratehaving a large diameter is preferably employed for higher productivity.In a case of using substrate 1 having a large diameter, however, warpagemainly caused by stress originating from difference in rate of thermalexpansion between substrate 1 and a nitride semiconductor layer becomesgreater, and consequently, breakage of substrate 1 or a crack in asurface of a nitride semiconductor layer is more likely. As will bedescribed later, the present invention can suppress breakage ofsubstrate 1 or a crack caused in a surface of a nitride semiconductorlayer even in a case of using substrate 1 having a large diameter notsmaller than 100 mm (approximately 4 inches).

Then, as shown in the schematic cross-sectional view in FIG. 2, recessportion 1 b and projection portion 1 a provided between recess portions1 b are formed at the surface of substrate 1.

FIG. 3 shows the schematic enlarged plan view of one example of thesurface of substrate 1 shown in FIG. 2. Here, an angle of each interiorangle of virtual triangle 1 t where projection portion 1 a is arrangedat each vertex is preferably not smaller than 50° and not greater than70° in the plan view of the surface of substrate 1. In this case, thirdnitride semiconductor underlying layer 3 tends to start growth on aregion of recess portion 1 b in a stable manner. Then, as first nitridesemiconductor underlying layer 4 formed on third nitride semiconductorunderlying layer 3 further grows, first nitride semiconductor underlyinglayer 4 tends to be able to form at least 6 first oblique facet planes 4r so as to surround projection portion 1 a on the outer side ofprojection portion 1 a with projection portion 1 a being located in thecenter.

Moreover, in the plan view of the surface of substrate 1, an intervalbetween adjacent projection portions 1 a is preferably not smaller than0.2 μm and not greater than 7 μm, more preferably not smaller than 1 μmand not greater than 3 μm, and further preferably around 2 μm. When aninterval between adjacent projection portions 1 a is not smaller than0.2 μm and not greater than 7 μm, a problem in terms of process tends tobe less. The problem in terms of process includes, for example, a longertime period of dry etching for increasing a height of projection portion1 a, an excessively long time period of growth required until uppersurface 5U of second nitride semiconductor underlying layer 5 iscompletely flat, and the like. It is noted herein that an intervalbetween adjacent projection portions 1 a means a shortest distancebetween adjacent projection portions 1 a.

In addition, in the plan view of the surface of substrate 1, a diameterof an annular circle of projection portion 1 a is preferably not smallerthan ½ and not greater than ¾ of an interval between adjacent projectionportions 1 a. For example, when an interval between adjacent projectionportions 1 a is 2 μm, a diameter of an annular circle of projectionportion 1 a is more preferably around 1.2 μm. When a diameter of anannular circle of projection portion 1 a is not smaller than ½ and notgreater than ¾ of an interval between adjacent projection portions 1 aand in particular around 1.2 μm, third nitride semiconductor underlyinglayer 3 tends to start growth on the region of recess portion 1 b in amanner more stable than on the region of projection portion 1 a.

Furthermore, a height of projection portion 1 a is preferably notsmaller than ¼ and not greater than 1 of a diameter of an annular circleof projection portion 1 a in the plan view of the surface of substrate1. For example, when a diameter of an annular circle of projectionportion 1 a is 1.2 μm, a height of projection portion 1 a is morepreferably around 0.6 μm. In this case, third nitride semiconductorunderlying layer 3 tends to start growth on the region of recess portion1 b in a manner more stable than on the region of projection portion 1a.

For example, as shown in FIG. 4 which is the schematic enlargedcross-sectional view along the line B-B passing through the center ofthe projection portion shown in FIG. 3, projection portion 1 a ispreferably in a shape having tip end portion 1 c. In a case where theupper surface of projection portion 1 a is flat, third nitridesemiconductor underlying layer 3 which will be described later may grownot only on recess portion 1 b but also on a flat upper surface ofprojection portion 1 a. On the other hand, in a case where projectionportion 1 a is in a shape having tip end portion 1 c, third nitridesemiconductor underlying layer 3 and first nitride semiconductorunderlying layer 4 selectively grow from recess portion 1 b and secondnitride semiconductor underlying layer 5 which successively grows meetsabove tip end portion 1 c of projection portion 1 a. Therefore, it isconsidered that a region where a crystal defect occurs is limited andthe number of defects as a whole can be decreased.

Then, as shown in the schematic cross-sectional view in FIG. 5, nitridesemiconductor intermediate layer 2 is formed on the surface of substrate1. Here, nitride semiconductor intermediate layer 2 can be formed, forexample, with reactive sputtering in which N₂ and Ar are introduced in achamber and an Al target is sputtered in a mixed atmosphere of N₂ andAr. Ar does not necessarily have to be introduced into the chamber. Inaddition, a trace amount of O₂ may be added as an introduction gas. Byusing an introduction gas containing a trace amount of O₂, a film betterin quality than nitride semiconductor intermediate layer 2 containingoxygen originating from remaining moisture in the chamber is obtained.

Then, as shown in a schematic cross-sectional view in FIG. 23, thirdnitride semiconductor underlying layer 3 is formed on the surface ofnitride semiconductor intermediate layer 2, and as shown in a schematiccross-sectional view in FIG. 24, first nitride semiconductor underlyinglayer 4 is formed on a surface of third nitride semiconductor underlyinglayer 3. In addition, as shown in a schematic cross-sectional view inFIG. 25, lower layer 5A of second nitride semiconductor underlying layer5 is formed on the surface of first nitride semiconductor underlyinglayer 4, and as shown in a schematic cross-sectional view in FIG. 26,upper layer 5B of second nitride semiconductor underlying layer 5 isformed on a surface of lower layer 5A of second nitride semiconductorunderlying layer 5.

Here, third nitride semiconductor underlying layer 3, first nitridesemiconductor underlying layer 4, and second nitride semiconductorunderlying layer 5 (lower layer 5A and upper layer 5B) can successivelybe formed on the surface of nitride semiconductor intermediate layer 2,for example, with MOCVD (Metal Organic Chemical Vapor Deposition).

More specifically, as shown in a schematic cross-sectional view in FIG.27, initially, third nitride semiconductor underlying layer 3 (forexample, having a thickness t₃=300 nm) is formed on the surface ofnitride semiconductor intermediate layer 2 mainly in recess portion 1 b,then first nitride semiconductor underlying layer 4 (for example, havinga thickness t₄=1400 nm) is formed at least on the surface of thirdnitride semiconductor underlying layer 3, and thereafter second nitridesemiconductor underlying layer 5 is formed at least on the surface offirst nitride semiconductor underlying layer 4. Here, second nitridesemiconductor underlying layer 5 is formed of a stack structure ofundoped lower layer 5A (for example, having a thickness t_(5A)=4000 nm)and n-type doped upper layer 5B (for example, having t_(5B)=a thicknessof 3000 nm).

A method of manufacturing second nitride semiconductor underlying layer5 having few crystal defects and flat upper surface 5U, in particular, agrowth mode, will now be described with reference to a schematiccross-sectional view in FIG. 28.

[Mode of Growth of Nitride Semiconductor Underlying Layer]

Initially, third nitride semiconductor underlying layer 3, first nitridesemiconductor underlying layer 4, and second nitride semiconductorunderlying layer 5 (hereinafter referred to as “each layer of thenitride semiconductor underlying layer”) are each grown in anappropriately selected growth mode. For the sake of convenience, thegrowth mode is herein defined as follows.

Two-dimensional growth mode: A growth mode in which a flat surface islikely to be obtained

Three-dimensional growth mode: A growth mode in which an oblique facetplane is likely to be formed

Two-point-five dimensional growth mode: A growth mode intermediatebetween the two-dimensional growth mode and the three-dimensional growthmode

[Relation Between Mode of Growth of Nitride Semiconductor UnderlyingLayer and Growth Parameter]

Then, switching between the growth modes used for growth of each layerof the nitride semiconductor underlying layer can be made byappropriately selecting three growth parameters of (A-2) a growthtemperature, (B-2) a growth pressure, and (C-2) a V/III ratio.

Specifically, at least one growth parameter of (A-2), (B-2), and (C-2)below or combination thereof can lead to realization. Here, as a resultof dedicated studies conducted by the present inventor, correlationbetween each of these three growth parameters and a mode of growth of anitride semiconductor underlying layer could be found.

(A-2) Growth Temperature

As a growth temperature is higher, the two-dimensional growth mode islikely to be set, and as a growth temperature is lower, thethree-dimensional growth mode is likely to be set.

(B-2) Growth Pressure

As a growth pressure is lower, the two-dimensional growth mode is likelyto be set, and as a growth pressure is higher, the three-dimensionalgrowth mode is likely to be set.

(C-2) V/III Ratio

As a V/III ratio is lower, the two-dimensional growth mode is likely tobe set, and as a V/III ratio is higher, the three-dimensional growthmode is likely to be set. It is noted that a V/III ratio represents aratio between a molar quantity of a group V source material gas suppliedper unit time during growth of a nitride semiconductor underlying layerand a molar quantity of a group III source material gas supplied perunit time.

Then, in order to form second nitride semiconductor underlying layer 5having few crystal defects, high crystallinity, and flat upper surface5U, initially, third nitride semiconductor underlying layer 3 is grownin the “2.5 dimensional growth mode” which is a growth mode intermediatebetween the “two-dimensional growth mode” in which a flat surface isobtained and the “three-dimensional growth mode” in which a crystalplane having an oblique facet preferentially appears.

Thus, the surface of third nitride semiconductor underlying layer 3 hasthird oblique facet plane 3 f and third flat region 3 c. Then, a ratioof area of third oblique facet plane 3 f at the surface of each thirdnitride semiconductor underlying layer 3 is lower than a ratio of areaof third flat region 3 c.

First nitride semiconductor underlying layer 4 is grown in the“three-dimensional growth mode” such that first oblique facet plane 4 ris formed.

Thus, the surface of first nitride semiconductor underlying layer 4 hasfirst oblique facet plane 4 r and first flat region 4 c. Then, a ratioof area of first oblique facet planes 4 r in the plan view of thesurface of each first nitride semiconductor underlying layer 4 is higherthan a ratio of area of first flat regions 4 c.

Furthermore, second nitride semiconductor underlying layer 5 is grown inthe “two-dimensional growth mode” in order to bury first oblique facetplane 4 r and form flat upper surface 5U.

Thus, second nitride semiconductor underlying layer 5 having few crystaldefects, high crystallinity, and flat upper surface 5U can be formed.

Namely, by providing third oblique facet plane 3 f at the surface ofthird nitride semiconductor underlying layer 3, dislocation extending ina direction of a c (layer) axis of a nitride semiconductor layer is bentin a direction of third oblique facet plane 3 f, so that the numberthereof is decreased.

Then, by providing first oblique facet planes 4 r at a ratio of areahigher than a ratio of area of first flat regions 4 c in the plan viewof the surface of first nitride semiconductor underlying layer 4,dislocation extending in the direction of the c (layer) axis of anitride semiconductor layer is bent in a direction of first obliquefacet plane 4 r, so that the number thereof is further decreased.

By thus growing second nitride semiconductor underlying layer 5 in thetwo-dimensional growth mode in which growth of a nitride semiconductorlayer having a flat surface is promoted on the surface of first nitridesemiconductor underlying layer 4 in which the number of dislocationsextending in the direction of the c (layer) axis of the nitridesemiconductor layer is decreased, second nitride semiconductorunderlying layer 5 having few crystal defects, good crystallinity, andflat upper surface 5U can be formed.

It is noted that, though second nitride semiconductor underlying layer 5is formed of a stack structure of lower layer 5A and upper layer 5B,lower layer 5A is an undoped layer and upper layer 5B can be grown bycarrying out doping with an n-type under the growth conditions basicallythe same as those for lower layer 5A.

Summarizing the results above, the step of forming third nitridesemiconductor underlying layer 3 and first nitride semiconductorunderlying layer 4 is preferably performed to satisfy at least onecondition selected from the group consisting of (i-2), (ii-2), and(iii-2) below. Thus, a nitride semiconductor underlying layer lesslikely to experience cracking and having a narrow half width of an X-rayrocking curve tends to be obtained.

(i-2) A growth temperature during growth of third nitride semiconductorunderlying layer 3 is set to be higher than a growth temperature duringgrowth of first nitride semiconductor underlying layer 4.

(ii-2) A pressure during growth of third nitride semiconductorunderlying layer 3 is set to be lower than a pressure during growth ofthe first nitride semiconductor underlying layer.

(iii-2) A V/III ratio of a gas supplied during growth of third nitridesemiconductor underlying layer 3 is set to be lower than a V/III ratioof a gas supplied during growth of first nitride semiconductorunderlying layer 4.

In addition, the step of forming third nitride semiconductor underlyinglayer 3, first nitride semiconductor underlying layer 4, and secondnitride semiconductor underlying layer 5 is preferably performed tosatisfy at least one condition selected from the group consisting of(I-2), (II-2), and (III-2) below and to satisfy at least one conditionselected from the group consisting of (a-2), (b-2), and (c-2) below.Thus, a nitride semiconductor underlying layer less likely to experiencecracking and having a narrow half width of an X-ray rocking curve tendsto be obtained.

(I-2) A growth temperature during growth of second nitride semiconductorunderlying layer 5 is set to be higher than a growth temperature duringgrowth of third nitride semiconductor underlying layer 3.

(II-2) A pressure during growth of second nitride semiconductorunderlying layer 5 is set to be lower than a pressure during growth ofthird nitride semiconductor underlying layer 3.

(III-2) A V/III ratio of a gas supplied during growth of second nitridesemiconductor underlying layer 5 is set to be lower than a V/III ratioof a gas supplied during growth of third nitride semiconductorunderlying layer 3.

(a-2) A growth temperature during growth of second nitride semiconductorunderlying layer 5 is set to be higher than a growth temperature duringgrowth of first nitride semiconductor underlying layer 4.

(b-2) A pressure during growth of second nitride semiconductorunderlying layer 5 is set to be lower than a pressure during growth offirst nitride semiconductor underlying layer 4.

(c-2) A V/III ratio of a gas supplied during growth of second nitridesemiconductor underlying layer 5 is set to be lower than a V/III ratioof a gas supplied during growth of first nitride semiconductorunderlying layer 4.

FIG. 29 shows a schematic enlarged plan view of one example of a surfaceof third nitride semiconductor underlying layer 3. As shown in FIG. 29,third nitride semiconductor underlying layer 3 has third oblique facetplane 3 f surrounding projection portion 1 a on the outer side ofprojection portion 1 a.

In addition, one third oblique facet plane 3 f surrounding projectionportion 1 a and another third oblique facet plane 3 f surroundingprojection portion 1 a are coupled to each other at third flat region 3c of third nitride semiconductor underlying layer 3.

Third oblique facet plane 3 f of third nitride semiconductor underlyinglayer 3 is inclined downward from third flat region 3 c of third nitridesemiconductor underlying layer 3 toward projection 1 a of substrate 1.

FIG. 30 shows a schematic enlarged plan view of another example of thesurface of third nitride semiconductor underlying layer 3. The exampleshown in FIG. 30 is characterized in that substantially the entiresurface of recess portion 1 b of substrate 1 is uniformly covered withthird flat region 3 c of third nitride semiconductor underlying layer 3and third oblique facet plane 3 f is slightly formed around projectionportion 1 a.

Namely, in the example shown in FIG. 30, as compared with the exampleshown in FIG. 29, a ratio of area occupied by third flat region 3 c inthe surface of third nitride semiconductor underlying layer 3 is higherthan a ratio of area occupied by third oblique facet plane 3 f.

FIG. 31 shows a schematic cross-sectional view along B-B in FIG. 30.Growth of third nitride semiconductor underlying layer 3 proceedsselectively from a region on recess portion 1 b of substrate 1. Then, asgrowth of third nitride semiconductor underlying layer 3 proceeds,substantially the entire surface of the region on recess portion 1 b ofsubstrate 1 is uniformly covered with third flat region 3 c of thirdnitride semiconductor underlying layer 3 and third facet plane 3 f isslightly formed around projection portion 1 a of substrate 1.

FIG. 32 shows a schematic enlarged plan view of another example of thesurface of third nitride semiconductor underlying layer 3. The exampleshown in FIG. 32 is characterized in that a rough surface region 3 d isformed at the surface of third nitride semiconductor underlying layer 3.Here, even in a case where third nitride semiconductor underlying layer3 has a layer thickness not smaller than 50 nm, third flat region 3 cand rough surface region 3 d rougher than third flat region 3 c arepresent together at the surface of third nitride semiconductorunderlying layer 3 in the region on the recess portion. In this case,disadvantageously, when first nitride semiconductor underlying layer 4is grown on the surface of this rough surface region 3 d, the surface offirst nitride semiconductor underlying layer 4 is likely to be a greaterrough surface, and the surface of second nitride semiconductorunderlying layer 5 grown further thereon is less likely to be flat.

Third nitride semiconductor underlying layer 3 is preferably grown undersuch a condition that a ratio of area of rough surface region 3 doccupying the surface of third nitride semiconductor underlying layer 3is not higher than 5%. In this case, first nitride semiconductorunderlying layer 4 and second nitride semiconductor underlying layer 5grown on the surface of third nitride semiconductor underlying layer 3each tend to be a film having few crystal defects and goodcrystallinity.

FIG. 33 shows a schematic enlarged plan view of one example of thesurface of first nitride semiconductor underlying layer 4 grown afterthird nitride semiconductor underlying layer 3 is formed. First nitridesemiconductor underlying layer 4 has 6 first oblique facet planes 4 rsurrounding projection portion 1 a on the outer side of projectionportion 1 a of substrate 1.

In the plan view shown in FIG. 33, two first oblique facet planes 4 rappear in the direction of the a (sub) axis and two first oblique facetplanes 4 r appear in each of the direction inclined by an angle of +60°with respect to the direction of the a (sub) axis and the directioninclined by an angle of −60° with respect to the direction of the a(sub) axis (both of which are the u directions) (this case beingreferred to as a “case 2-1”).

More specifically, in the plan view of the surface of first nitridesemiconductor underlying layer 4 shown in FIG. 33, two first obliquefacet planes 4 r which appear in the direction of the a (sub) axis among6 first oblique facet planes 4 r are inclined obliquely upward withrespect to the direction of the a (sub) axis (<11-20> direction), andfirst oblique facet plane 4 r extends in that direction of inclination.

In addition, similarly, in the plan view of the surface of first nitridesemiconductor underlying layer 4, two first oblique facet planes 4 rwhich appear in each of the direction inclined by an angle of +60° withrespect to the direction of the a (sub) axis and the direction inclinedby an angle of −60° with respect to the direction of the a (sub) axis(both of which are the u directions) are also inclined obliquely upwardwith respect to the direction inclined by an angle of +60° with respectto the direction of the a (sub) axis and the direction inclined by anangle of −60° with respect to the direction of the a (sub) axis, andfirst oblique facet plane 4 r extends in that direction of inclination.

FIG. 34 shows a schematic cross-sectional view along B-B in FIG. 33.First oblique facet plane 4 r which appears in FIG. 34 is a plane whichsimilarly appears also in a direction of depth of a cross-sectionthereof in a range where first oblique facet planes 4 r are present.

In addition, one first oblique facet plane 4 r surrounding projectionportion 1 a and another first oblique facet plane 4 r surroundingprojection portion 1 a are coupled to each other at upper surface 4 c offirst nitride semiconductor underlying layer 4.

Here, 6 first oblique facet planes 4 r surrounding an outercircumference of projection portion 1 a are inclined by each extendingobliquely upward from projection portion 1 a.

FIG. 35 shows a schematic enlarged plan view of another example of thesurface of first nitride semiconductor underlying layer 4 grown afterthird nitride semiconductor underlying layer 3 is formed. The exampleshown in FIG. 35 shows positional relation between first oblique facetplane 4 r and first flat region 4 c of first nitride semiconductorunderlying layer 4 in a case where projection portions 1 a at thesurface of substrate 1 are arranged in a direction inclined by +30° withrespect to the direction of the a (sub) axis and in a direction inclinedby −30° with respect to the direction of the a (sub) axis (this casebeing referred to as a “case 2-2”).

In a case of growing first nitride semiconductor underlying layer 4 inthe three-dimensional growth mode in which 6 first oblique facet planes4 r are formed, first oblique facet planes 4 r and first flat region 4 cof first nitride semiconductor underlying layer 4 are each more likelyto be affected by arrangement of projection portions 1 a at substrate 1.

In case 2-2, in the plan view of the surface of first nitridesemiconductor underlying layer 4, a shape of first flat region 4 c offirst nitride semiconductor underlying layer 4 is in such a shape ascontinuing triangles, and second nitride semiconductor underlying layer5 is formed on first flat region 4 c after switching to thetwo-dimensional growth mode, which is a mode of growth of second nitridesemiconductor underlying layer 5, has been made. Since crystal defectsat first flat region 4 c of first nitride semiconductor underlying layer4 tend to be taken over by and propagate through second nitridesemiconductor underlying layer 5, case 2-1 in which an area of firstflat region 4 c occupied in the surface of first nitride semiconductorunderlying layer 4 is smaller tends to bring about a film having fewcrystal defects and better crystallinity in second nitride semiconductorunderlying layer 5, as compared with case 2-2.

Thickness t₃ of third nitride semiconductor underlying layer 3 shown inFIG. 27 is preferably not smaller than 60 nm and not greater than aheight of projection portion 1 a (for example, not greater than 600 nmin a case where projection portion 1 a has a height of 0.6μm). Whenthickness t₃ is not smaller than 60 nm, third nitride semiconductorunderlying layer 3 covers the entire region of nitride semiconductorintermediate layer 2 in recess portion 1 b, and consequently firstnitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 each tend to be a film having fewcrystal defects and good crystallinity. When thickness t₃ is not greaterthan a height of projection portion 1 a, first oblique facet plane 4 ris likely to be formed during growth of first nitride semiconductorunderlying layer 4, and hence first nitride semiconductor underlyinglayer 4 and second nitride semiconductor underlying layer 5 each tend toreadily be a film having few crystal defects and good crystallinity.

In addition, a thickness t₃₄ of a largest thickness portion of a filmwhich is combination of third nitride semiconductor underlying layer 3and first nitride semiconductor underlying layer 4 shown in FIG. 27 ispreferably not less than 0.5 time and not more than 2 times as great asan interval between adjacent projection portions 1 a in the plan view ofthe surface of substrate 1. For example, when an interval betweenadjacent projection portions 1 a in the plan view of the surface ofsubstrate 1 is 2 μm, thickness t₃₄ is preferably not smaller than 1 μmand not greater than 4 μm. When thickness t₃₄ is equal to or more than0.5 time as great as the interval between adjacent projection portions 1a in the plan view of the surface of substrate 1, a ratio of area offirst oblique facet planes 4 r at the surface of first nitridesemiconductor underlying layer 4 is further higher than a ratio of areaof first flat regions 4 c, and therefore first nitride semiconductorunderlying layer 4 and second nitride semiconductor underlying layer 5each tend to readily be a film having few crystal defects and goodcrystallinity. Alternatively, when thickness t₃₄ is equal to or lessthan 2 times as great as the interval between adjacent projectionportions 1 a in the plan view of the surface of substrate 1, tendency tobury projection portion 1 a while first oblique facet 4 r is formed islow, and hence crystal defects do not tend to remain above projectionportion 1 a.

A thickness of second nitride semiconductor underlying layer 5 (a totalthickness of thickness t_(5A) of lower layer 5A and thickness t_(5B) ofupper layer 5B) is preferably at least twice a height of projectionportion 1 a. For example, when a height of projection portion 1 a is 0.6μm, the thickness is preferably not smaller than 1.2 μm. When athickness of second nitride semiconductor underlying layer 5 is at leasttwice the height of projection portion 1 a, tendency that lower layer 5Aof second nitride semiconductor underlying layer 5 can bury projectionportion 1 a is higher, and hence tendency that upper surface 5M of lowerlayer 5A of second nitride semiconductor underlying layer 5 is flat ishigher.

It is noted that, for example, a layer composed of a group III nitridesemiconductor expressed with a formula Al_(x10)Ga_(y10)In_(z10)N(0≦x10≦1, 0≦y10≦1, 0≦z10≦1, x10+y10+z10≠0) can be employed as thirdnitride semiconductor underlying layer 3. In addition, preferably, thirdnitride semiconductor underlying layer 3, first nitride semiconductorunderlying layer 4, and second nitride semiconductor underlying layer 5are identical in composition in terms of a material and they aredifferent only in growth conditions.

At the time of switching from the growth mode during growth of thirdnitride semiconductor underlying layer 3 to the growth mode duringgrowth of first nitride semiconductor underlying layer 4 and switchingfrom the growth mode during growth of first nitride semiconductorunderlying layer 4 to the growth mode during growth of second nitridesemiconductor underlying layer 5, preferably, a growth interruption timeperiod, for example, approximately for 2 seconds to 60 seconds, isprovided during which growth conditions are changed, however, conditionsmay be changed continuously.

In order not to take over such a crystal defect as dislocation innitride semiconductor intermediate layer 2 made of an aggregate ofcolumn crystals, a nitride semiconductor layer containing Ga as a groupIII element is preferably employed for third nitride semiconductorunderlying layer 3, first nitride semiconductor underlying layer 4, andsecond nitride semiconductor underlying layer 5.

In order not to take over dislocation into nitride semiconductorintermediate layer 2, dislocation loop should be formed around aninterface with nitride semiconductor intermediate layer 2. In a casewhere third nitride semiconductor underlying layer 3 is composed of agroup III nitride semiconductor containing Ga, dislocation loop islikely to be formed. Then, by employing third nitride semiconductorunderlying layer 3, first nitride semiconductor underlying layer 4, andsecond nitride semiconductor underlying layer 5 each composed of a groupIII nitride semiconductor containing Ga, dislocation is confined as aloop around the interface with nitride semiconductor intermediate layer2, so that taking over of dislocation from nitride semiconductorintermediate layer 2 into first nitride semiconductor underlying layer 4tends to be suppressed.

In addition, the surface of nitride semiconductor intermediate layer 2immediately before third nitride semiconductor underlying layer 3 isformed may be subjected to heat treatment. Through this heat treatment,a cleaner surface and improvement in crystallinity of nitridesemiconductor intermediate layer 2 tend to be achieved. This heattreatment can be carried out, for example, in an MOCVD apparatus inwhich MOCVD is employed, and for example, a hydrogen gas, a nitrogengas, or the like can be employed as an atmospheric gas during heattreatment.

Moreover, in order to prevent decomposition of nitride semiconductorintermediate layer 2 during heat treatment above, an ammonia gas may bemixed with the atmospheric gas during heat treatment. Furthermore, heattreatment above can be carried out, for example, at a temperature notlower than 900° C. and not higher than 1250° C., for example, for a timeperiod not shorter than 1 minute and not longer than 60 minutes.

Preferably, third nitride semiconductor underlying layer 3, firstnitride semiconductor underlying layer 4, and lower layer 5A of secondnitride semiconductor underlying layer 5 are each undoped, and upperlayer 5B of second nitride semiconductor underlying layer 5 is dopedwith an n-type, however, third nitride semiconductor underlying layer 3,first nitride semiconductor underlying layer 4, and lower layer 5A ofsecond nitride semiconductor underlying layer 5 may each be doped withan n-type. In a case of doping with an n-type, doping with an n-typedopant in a range not lower than 1×10¹⁷ cm⁻³ and not higher than 1×10¹⁹cm⁻³ may be carried out.

For example, at least one or the like selected from the group consistingof silicon, germanium, and tin can be employed as an n-type dopant, andamong these, use of silicon is preferred. In a case of using silicon asan n-type dopant, a silane gas or a disilane gas is preferably used asan n-type doping gas.

A temperature of substrate 1 during growth of each of third nitridesemiconductor underlying layer 3, first nitride semiconductor underlyinglayer 4, and second nitride semiconductor underlying layer 5 ispreferably not lower than 800° C. and not higher than 1250° C. and morepreferably not lower than 900° C. and not higher than 1150° C. When atemperature of substrate 1 during growth of each of third nitridesemiconductor underlying layer 3, first nitride semiconductor underlyinglayer 4, and second nitride semiconductor underlying layer 5 is notlower than 800° C. and not higher than 1250° C. and in particular notlower than 900° C. and not higher than 1150° C., third nitridesemiconductor underlying layer 3, first nitride semiconductor underlyinglayer 4, and second nitride semiconductor underlying layer 5 having fewcrystal defects and excellent crystallinity tends to be grown.

Then, for example, with MOCVD, n-type nitride semiconductor contactlayer 7 is formed on the surface of second nitride semiconductorunderlying layer 5. It is noted that n-type nitride semiconductorcontact layer 7 should only be provided such that at least a partthereof is in contact with the surface of second nitride semiconductorunderlying layer 5.

A total thickness of third nitride semiconductor underlying layer 3,first nitride semiconductor underlying layer 4, second nitridesemiconductor underlying layer 5, and n-type nitride semiconductorcontact layer 7 is preferably not smaller than 4 μm and not greater than20 μm and more preferably not smaller than 4 μm and not greater than 15μm. When a total thickness of third nitride semiconductor underlyinglayer 3, first nitride semiconductor underlying layer 4, second nitridesemiconductor underlying layer 5, and n-type nitride semiconductorcontact layer 7 is not smaller than 4 μm, crystallinity of these layerstends to be good and a pit does not tend to be caused in a surface ofthese layers. On the other hand, when a total thickness of third nitridesemiconductor underlying layer 3, first nitride semiconductor underlyinglayer 4, second nitride semiconductor underlying layer 5, and n-typenitride semiconductor contact layer 7 is not greater than 15 μm, warpageof substrate 1 does not become great, breakage of a wafer or unevenexposure during a photolithography process is less likely, and yield ofan element tends to be high. Furthermore, when a total thickness ofthird nitride semiconductor underlying layer 3, first nitridesemiconductor underlying layer 4, second nitride semiconductorunderlying layer 5, and n-type nitride semiconductor contact layer 7 isin particular not smaller than 4 μm and not greater than 15 μm,crystallinity of these layers tends to be good, occurrence of warpage ofsubstrate 1 tends to be suppressed, and lowering in yield of an elementtends to further effectively be prevented. It is noted that an upperlimit of a thickness of n-type nitride semiconductor contact layer 7 ofthe total thickness of these layers is not particularly limited.

Then, for example, with MOCVD, n-type nitride semiconductor superlatticelayer 92 is formed on the surface of n-type nitride semiconductorcontact layer 7. A main function of n-type nitride semiconductorsuperlattice layer 92 is to suppress extension of a crystal defectextending from below to above of n-type nitride semiconductor contactlayer 7 as far as nitride semiconductor active layer 11, by using aninterface between layers forming the superlattice of n-type nitridesemiconductor superlattice layer 92.

For example, a superlattice structure obtained by alternately stacking10 pairs of a low band gap layer composed, for example, ofIn_(x11)Ga_(1-x11)N (0<x11≦1, for example, x111=0.02) and having athickness of 2.5 nm and a high band gap layer composed, for example, ofGaN and having a thickness of 2.5 nm can be employed as n-type nitridesemiconductor superlattice layer 92, however, composition of the lowband gap layer and the high band gap layer is not limited thereto. Sincethe low band gap layer contains volatile In as its composition, a growthtemperature for entire n-type nitride semiconductor superlattice layer92 or at least for the low band gap layer is preferably lower than thatfor n-type nitride semiconductor contact layer 7. Though a growthtemperature may be constant, for example, growth may be carried out at alow temperature for the low band gap layer, and growth may be carriedout at a high temperature for the high band gap layer. It is noted thatn-type nitride semiconductor superlattice layer 92 may be omitted andnitride semiconductor active layer 11 may be formed on n-type nitridesemiconductor contact layer 7. In this case, since an element structureis simplified, variation in characteristics tends to be lowered.

Any one or both of the low band gap layer and the high band gap layer inn-type nitride semiconductor superlattice layer 92 is/are preferablydoped with an n-type. Concentration of doping with an n-type dopant ispreferably not lower than 1×10¹⁷ cm⁻³ and not higher than 1×10²° cm³,more preferably not lower than 1×10¹⁸ cm⁻³ and not higher than 1×10¹⁹cm⁻³, and further preferably not lower than 2×10¹⁸ cm⁻³ and not higherthan 4×10¹⁸ cm⁻³. In this case, good crystallinity of n-type nitridesemiconductor superlattice layer 92 tends to be maintained and anoperation voltage of an element tends to be lowered.

Then, for example, with MOCVD, nitride semiconductor active layer 11,p-type nitride semiconductor clad layer 13, and p-type nitridesemiconductor contact layer 15 are formed on the surface of n-typenitride semiconductor superlattice layer 92 in this order.

Then, light transmitting electrode layer 19 composed, for example, ofITO (Indium Tin Oxide) is formed on the surface of p-type nitridesemiconductor contact layer 15.

Then, a part of the surface of n-type nitride semiconductor contactlayer 7 is exposed by etching away a part of a stack structure afterp-side electrode 21 is formed.

Then, p-side electrode 21 and n-side electrode 20 are simultaneouslyformed on the surface of light-transmitting electrode 19 and on theexposed surface of n-type nitride semiconductor contact layer 7,respectively. For example, a stack film of a nickel layer, an aluminumlayer, a titanium layer, and a gold layer can be formed as p-sideelectrode 21 and n-side electrode 20.

It is noted that, instead of simultaneously forming p-side electrode 21and n-side electrode 20, they may separately be formed, and in thatcase, a material optimal for p-side electrode 21 and n-side electrode 20can be selected by varying a material for each of these electrodes.

Thereafter, insulating protection film 23 composed of SiO₂ or the likeis formed on the entire surface of the stack structure after n-sideelectrode 20 is formed, an opening is provided in insulating protectionfilm 23 so as to expose p-side electrode 21 and n-side electrode 20, anda wafer on which a plurality of nitride semiconductor light emittingdiode elements 200 are formed is divided into individual elements, sothat nitride semiconductor light emitting diode element 200 according toEmbodiment 2-1 can be fabricated.

In nitride semiconductor light emitting diode element 200 according toEmbodiment 2-1 fabricated as above, on the surface of nitridesemiconductor intermediate layer 2 provided on the surface of substrate1, third nitride semiconductor underlying layer 3 is grown in the 2.5dimensional growth mode, first nitride semiconductor underlying layer 4is grown in the three-dimensional growth mode, and second nitridesemiconductor underlying layer 5 is grown in the two-dimensional growthmode. N-type nitride semiconductor contact layer 7, n-type nitridesemiconductor superlattice layer 92, nitride semiconductor active layer11, p-type nitride semiconductor clad layer 13, and p-type nitridesemiconductor contact layer 15 are stacked in this order on flat uppersurface 5U of second nitride semiconductor underlying layer 5 thusobtained, which has a narrow half width of an X-ray rocking curve andgood crystallinity. Therefore, each layer on the nitride semiconductorunderlying layer such as nitride semiconductor active layer 11 is low indislocation density and excellent in crystallinity.

Therefore, nitride semiconductor light emitting diode element 200according to Embodiment 2-1 formed of such a nitride semiconductor layerhaving excellent crystallinity is an element low in operation voltageand high in emission output.

Nitride semiconductor light emitting diode element 200 according toEmbodiment 2-1 was adopted as a bare chip (not sealed with resin as willbe described later) evaluation element, and a current of 30 mA was fedto 10 elements. Then, it was confirmed that an element low in operationvoltage and high in emission output, which achieved light output of 41mW, an operation voltage of 3.0 V, and an emission wavelength of 445 nmon average, was obtained.

FIG. 36 shows a schematic cross-sectional view of one example of a lightemitting device 210 including nitride semiconductor light emitting diodeelement 200 according to Embodiment 2-1.

Here, light emitting device 210 has such a construction that nitridesemiconductor light emitting diode element 200 according to Embodiment2-1 is set on second lead frame 31. Then, p-side electrode 21 of nitridesemiconductor light emitting diode element 200 and first lead frame 30are electrically connected to each other through first wire 33, andn-side electrode 20 of nitride semiconductor light emitting diodeelement 200 and second lead frame 31 are electrically connected to eachother through second wire 34. In addition, since nitride semiconductorlight emitting diode element 200 is molded with transparent moldingresin 35, light emitting device 210 is in a shape of a cannonball. Sincelight emitting device 210 having the construction shown in FIG. 36includes nitride semiconductor light emitting diode element 200according to Embodiment 2-1, a light emitting device low in operationvoltage and high in emission output can be achieved.

Embodiment 2-2

Embodiment 2 is characterized by being directed to a nitridesemiconductor transistor element which is an electronic device includingthe nitride semiconductor structure according to Embodiment 1 (a stackstructure of substrate 1, nitride semiconductor intermediate layer 2,third nitride semiconductor underlying layer 3, first nitridesemiconductor underlying layer 4, and second nitride semiconductorunderlying layer 5).

FIG. 37 shows a schematic cross-sectional view of a nitridesemiconductor transistor element 400 according to Embodiment 2-2.Nitride semiconductor transistor element 400 has a nitride semiconductorstructure constituted of substrate 1 formed of a sapphire substratehaving a c plane as a main surface, in which projection portions 1 a arearranged in three equivalent directions of the a (sub) axis, as well asnitride semiconductor intermediate layer 2 composed of AlN or the like,third nitride semiconductor underlying layer 3 composed of undoped GaNor the like, first nitride semiconductor underlying layer 4 composed ofundoped GaN or the like, and second nitride semiconductor underlyinglayer 5 composed of undoped GaN or the like, which are successivelystacked on the surface of substrate 1.

Then, nitride semiconductor electron transit layer 71 composed ofundoped GaN or the like is stacked on flat surface 5U of second nitridesemiconductor underlying layer 5 having few crystal defects and goodcrystallinity, and n-type nitride semiconductor electron supply layer 73composed of n-type AlGaN or the like is stacked on the surface ofnitride semiconductor electron transit layer 71.

Gate electrode 77 is provided on the surface of n-type nitridesemiconductor electron supply layer 73, and source contact layer 75S anddrain contact layer 75D composed of n-type GaN or the like are providedon respective opposing sides of gate electrode 77. In addition, sourceelectrode 78S is provided on source contact layer 75S, and drainelectrode 78D is provided on drain contact layer 75D.

One example of a method of manufacturing nitride semiconductortransistor element 400 according to Embodiment 2-2 will be describedbelow. Initially, as in Embodiment 2-1, nitride semiconductorintermediate layer 2 composed of AlN is formed with reactive sputteringon the surface of substrate 1 having projection portions 1 a and recessportions 1 b.

Then, on the surface of nitride semiconductor intermediate layer 2, withMOCVD, third nitride semiconductor underlying layer 3 composed ofundoped GaN is grown in the 2.5 dimensional growth mode in which thirdoblique facet plane 3 f and third flat region 3 c appear and firstnitride semiconductor underlying layer 4 composed of undoped GaN isgrown in the three-dimensional growth mode.

Here, first nitride semiconductor underlying layer 4 is grown under suchconditions that, in the plan view of the surface of first nitridesemiconductor underlying layer 4, two first oblique facet planes 4 rwhich appear in the direction of the a (sub) axis and two first obliquefacet planes 4 r which appear in each of the direction inclined by anangle of +60° with respect to the direction of the a (sub) axis and thedirection inclined by an angle of −60° with respect to the direction ofthe a (sub) axis appear.

Then, second nitride semiconductor underlying layer 5 composed ofundoped GaN is grown on the surface of first nitride semiconductorunderlying layer 4 in the two-dimensional growth mode with MOCVD. Here,second nitride semiconductor underlying layer 5 is grown under suchconditions that first oblique facet plane 4 r of first nitridesemiconductor underlying layer 4 is buried and flat upper surface 5Uappears.

Then, with MOCVD, nitride semiconductor electron transit layer 71composed of n-type Al_(x)Ga_(1-x)N is stacked on flat upper surface 5Uof second nitride semiconductor underlying layer 5, and n-type nitridesemiconductor electron supply layer 73 is stacked on the surface ofnitride semiconductor electron transit layer 71.

Thereafter, as shown in FIG. 37, after source contact layer 75S anddrain contact layer 75D are formed on the surface of n-type nitridesemiconductor electron supply layer 73, source electrode 78S, drainelectrode 78D, and gate electrode 77 are each formed. Nitridesemiconductor transistor element 400 according to Embodiment 2-2 can befabricated as above.

In nitride semiconductor transistor element 400 according to Embodiment2-2, in the plan view of the surface of first nitride semiconductorunderlying layer 4, first nitride semiconductor underlying layer 4 isgrown under such conditions that two first oblique facet planes 4 rwhich appear in the direction of the a (sub) axis and two first obliquefacet planes 4 r which appear in each of the direction inclined by anangle of +60° with respect to the direction of the a (sub) axis and thedirection inclined by an angle of −60° with respect to the direction ofthe a (sub) axis appear. Thus, since crystal defects in atwo-dimensional electron transit region at an uppermost surface ofnitride semiconductor electron transit layer 71 are decreased inparticular, electron mobility can be improved.

Therefore, in nitride semiconductor transistor element 400 according toEmbodiment 2-2 as well, each layer stacked on the surface of nitridesemiconductor intermediate layer 2 can be a layer low in dislocationdensity and excellent in crystallinity, and hence an element achievingimproved characteristics such as electron mobility can be obtained.

As above, according to the present embodiment, on the surface ofsubstrate 1 having projection portions 1 a and recess portions 1 b,initially, third nitride semiconductor underlying layer 3 is grown inthe 2.5 dimensional growth mode, then first nitride semiconductorunderlying layer 4 is grown in the three-dimensional growth mode, andthereafter second nitride semiconductor underlying layer 5 is grown inthe two-dimensional growth mode, so that second nitride semiconductorunderlying layer 5 serves as an underlying layer low in dislocationdensity and excellent in crystallinity.

Thus, while occurrence of breakage and crack of a wafer during growthwith MOCVD of a nitride semiconductor layer stacked on upper surface 5Uof second nitride semiconductor underlying layer 5 and in subsequentprocesses is suppressed, crystallinity expressed with a half width of anX-ray rocking curve or the like of a nitride semiconductor layer can beimproved and defect density expressed with the CL method, EPD, or thelike can be lowered. Therefore, a nitride semiconductor elementachieving improved device characteristics represented by emissionefficiency, electron mobility, and the like and a nitride semiconductorstructure serving as a basis for the nitride semiconductor element canbe provided.

Though only a layer formed with sputtering has been described as nitridesemiconductor intermediate layer 2, the method is not limited to thismethod, and for example, what is called a low-temperature buffer layerformed at a low temperature with MOCVD may be adopted. In addition, in acase of using a GaN substrate as substrate 1, nitride semiconductorintermediate layer 2 may be omitted.

It is noted that description other than the above in Embodiments 2-1 and2-2 is the same as that in Embodiments 1-1 and 1-2 and hence descriptionthereof will not be provided.

Embodiment 3-1

A method of manufacturing a nitride semiconductor structure according toEmbodiment 3-1 will be described below. The method of manufacturing anitride semiconductor structure according to Embodiment 3-1 ischaracterized in growing a first nitride semiconductor underlying layerwith MOCVD in a vertical MOCVD apparatus in which a carrier gascontaining a hydrogen gas is employed while a substrate is rotated andlimiting the number of rotations of the substrate per unit time and avolume ratio of the hydrogen gas to the total volume of the carrier gas.In addition, the method of manufacturing a nitride semiconductorstructure according to the present embodiment may naturally includeother steps between steps which will be described later.

Initially, as shown in a schematic cross-sectional view in FIG. 38, thestep of preparing substrate 1 is performed. Here, substrate 1 composedof trigonal corundum or hexagonal crystal can be prepared as substrate1. For example, a substrate made of sapphire (Al₂O₃) single crystal, AlNsingle crystal, GaN single crystal, or the like can be employed assubstrate 1 composed of trigonal corundum or hexagonal crystal.

In addition, a surface 40 of substrate 1 may be a c plane or a surfaceinclined with respect to the c plane by 5° or smaller, and a directionof inclination may be, for example, only in the direction of the m (sub)axis (<1-100>), only in the direction of the a (sub) axis (<11-20>), orin a direction which is combination of both of these directions. Morespecifically, such a substrate that surface 40 of substrate 1 isinclined by 0.15° to 0.35° in the direction of the m (sub) axis <1-100>of the substrate with respect to the c plane (a plane of which normal isthe c axis) or the like can be prepared as substrate 1.

Then, as shown in a schematic cross-sectional view in FIG. 39, recessportion 1 b and projection portion 1 a provided between recess portions1 b are formed at surface 40 of substrate 1. Such projection portions 1a and recess portions 1 b at the surface of substrate 1 can be formed,for example, through a process including a patterning step of forming amask defining two-dimensional arrangement of projection portions 1 a onsurface 40 of substrate 1 and a step of forming recess portions 1 b byetching surface 40 of substrate 1 with the use of the mask formed in thepatterning step. Here, the patterning step can be performed with acommon photolithography step. An etching step can be performed, forexample, with dry etching or wet etching. In order that a shape ofprojection portion 1 a has a tip end portion which will be describedlater, however, dry etching with which a shape of projection portion 1 ais readily controlled is preferably carried out.

Then, as shown in the schematic cross-sectional view in FIG. 5, nitridesemiconductor intermediate layer 2 is formed on the surface of substrate1.

Then, as shown in the schematic cross-sectional view in FIG. 6, firstnitride semiconductor underlying layer 4 is formed on the surface ofnitride semiconductor intermediate layer 2, and as shown in theschematic cross-sectional view in FIG. 7, second nitride semiconductorunderlying layer 5 is formed on the surface of first nitridesemiconductor underlying layer 4.

Here, first nitride semiconductor underlying layer 4 and second nitridesemiconductor underlying layer 5 can successively be formed on thesurface of nitride semiconductor intermediate layer 2, for example, withMOCVD with the use of a vertical MOCVD apparatus, in which a carrier gascontaining a hydrogen gas and a source material gas containing a groupIII source material gas and a group V source material gas are suppliedwhile substrate 1 on which nitride semiconductor intermediate layer 2has been formed is rotated.

First nitride semiconductor underlying layer 4 is grown in the facetgrowth mode in which first oblique facet plane 4 r is formed, and secondnitride semiconductor underlying layer 5 is grown in the embedmentgrowth mode in which first oblique facet plane 4 r is buried such thatfirst oblique facet plane 4 r and lower surface 5 b are in contact witheach other and flat upper surface 5 a is formed. Thus, second nitridesemiconductor underlying layer 5 having few crystal defects, highcrystallinity, and flat upper surface 5 a can be formed.

FIG. 8 shows the schematic enlarged plan view of one example of thesurface of first nitride semiconductor underlying layer 4 shown in FIG.6. As shown in FIG. 8, first nitride semiconductor underlying layer 4has 6 first oblique facet planes 4 r surrounding projection portion 1 aon the outer side of projection portion 1 a. In the plan view shown inFIG. 8, two first oblique facet planes 4 r appear in the direction ofthe a (sub) axis and two first oblique facet planes 4 r appear in eachof the direction inclined by an angle of +60° with respect to thedirection of the a (sub) axis and the direction inclined by an angle of−60° with respect to the direction of the a (sub) axis (both of whichare the u direction) (this case being referred to as a case 3-1). Inaddition, first oblique facet plane 4 r which appears in a cross-sectionalong the line B-B in FIG. 8 is a plane which similarly appears also ina direction of depth of a cross-section thereof in a range where firstoblique facet planes 4 r are present.

Furthermore, one first oblique facet plane 4 r surrounding projectionportion 1 a and another first oblique facet plane 4 r surroundingprojection portion 1 a are coupled to each other at upper surface 4 c offirst nitride semiconductor underlying layer 4.

First oblique facet plane 4 r of first nitride semiconductor underlyinglayer 4 is inclined downward from upper surface 4 c of first nitridesemiconductor underlying layer 4 toward projection 1 a of substrate 1.Here, among 6 first oblique facet planes 4 r, in the plan view of thesurface of first nitride semiconductor underlying layer 4, two firstoblique facet planes 4 r which appear in the direction of the a (sub)axis are inclined obliquely upward with respect to the direction of thea (sub) axis (<11-20> direction), and the facet plane extends in thedirection of inclination. In addition, similarly, in the plan view ofthe surface of first nitride semiconductor underlying layer 4, two firstoblique facet planes 4 r which appear in each of the direction inclinedby an angle of +60° with respect to the direction of the a (sub) axisand the direction inclined by an angle of −60° with respect to thedirection of the a (sub) axis are also inclined obliquely upward withrespect to the direction inclined by an angle of +60° with respect tothe direction of the a (sub) axis and the direction inclined by an angleof −60° with respect to the direction of the a (sub) axis, and the facetplane extends in the direction of inclination.

In addition, first oblique facet planes 4 r of first nitridesemiconductor underlying layer 4 serve as 6 facet planes surroundingprojection portion 1 a on the outer side of projection portion 1 a withprojection portion 1 a being located in the center, on nitridesemiconductor intermediate layer 2.

Moreover, in the plan view of the surface of first nitride semiconductorunderlying layer 4, substantially no facet plane other than firstoblique facet planes 4 r which appear in the direction of the a (sub)axis and the u directions preferably appears. More specifically, a ratioof area of first oblique facet planes 4 r expressed with the expression(I) above is preferably not lower than 80% and more preferably not lowerthan 90%. When a ratio of area of first oblique facet planes 4 r is notlower than 80% and in particular not lower than 90%, occurrence ofbreakage and crack of a wafer tends to be suppressed during growth of anitride semiconductor layer stacked on upper surface 5 a of secondnitride semiconductor underlying layer 5 and in subsequent processes.Furthermore, crystallinity of a nitride semiconductor layer expressedwith a half width of an X-ray rocking curve or the like also tends toimprove. Additionally, defect density which can be evaluated based on acathode luminescence method, etch pit density, or the like also tends tolower. Specifically, a half width (arcsec) of an X-ray rocking curve atthe (004) plane of a GaN underlying layer can be 30 to 40 arcsec.Further, dark spot density obtained with the CL method can be not higherthan 2×10⁸ cm⁻³.

The facet growth mode for first nitride semiconductor underlying layer 4in which first oblique facet plane 4 r as described above appears can berealized by setting the number of rotations per unit time of substrate 1during growth of first nitride semiconductor underlying layer 4 withMOCVD with the use of the vertical MOCVD apparatus to be not lower than400 RPM and not higher than 1000 RPM and setting a volume ratio of ahydrogen gas to the total volume of a carrier gas supplied during growthwith MOCVD of first nitride semiconductor underlying layer 4 to be notlower than 0.7 and not higher than 1.

This is because the present inventor has found as a result of dedicatedstudies the fact that, in growing first nitride semiconductor underlyinglayer 4 on nitride semiconductor intermediate layer 2 formed on thesurface of substrate 1 having projection portions and recess portionswith MOCVD with the use of the vertical MOCVD apparatus, the number ofrotations of substrate 1 per unit time is set to be not lower than 400RPM and not higher than 1000 RPM and a volume ratio of a hydrogen gas tothe total volume of a carrier gas supplied during growth of firstnitride semiconductor underlying layer 4 is not lower than 0.7 and nothigher than 1, so that first nitride semiconductor underlying layer 4can be a continuous film having high uniformity and having continuoussurfaces.

In a case where second nitride semiconductor underlying layer 5 is grownwith MOCVD on the surface of first nitride semiconductor underlyinglayer 4 which is such a continuous film, upper surface 5 a of secondnitride semiconductor underlying layer 5 having few crystal defects,high crystallinity, and high flatness can be obtained. Therefore, in thepresent embodiment, on upper surface 5 a of second nitride semiconductorunderlying layer 5 having such high crystallinity and high flatness, anitride layer having excellent crystallinity can be formed with goodreproducibility.

It is noted that “RPM” is abbreviation of “Rotation Per Minute,” andrefers to the number of rotations of substrate 1 per minute. Inaddition, the “vertical MOCVD apparatus” is a reaction furnace in whicha source material gas is supplied in a direction substantiallyperpendicular to a substrate surface.

The facet growth mode for first nitride semiconductor underlying layer 4where first oblique facet plane 4 r as described above appears and theembedment growth mode for second nitride semiconductor underlying layer5 in which first oblique facet plane 4 r is buried to form upper surface5 a high in flatness are preferably carried out to satisfy at least onecondition selected from the group consisting of (i-3), (ii-3), (iii-3),(iv-3), and (v-3) below and further preferably carried out to satisfyall conditions of (i-3), (ii-3), (iii-3), (iv-3), and (v-3) below. Inthe case where the facet growth mode for first nitride semiconductorunderlying layer 4 and the embedment growth mode for second nitridesemiconductor underlying layer 5 are carried out under the conditionsatisfying at least one of (i-3) to (v-3) below, in particular under theconditions satisfying all of (i-3) to (v-3), upper surface 5 a of secondnitride semiconductor underlying layer 5 having higher crystallinity andflatness can be obtained and hence a nitride layer having bettercrystallinity tends to be formed thereon with better reproducibility.

(i-3) A growth temperature during growth of first nitride semiconductorunderlying layer 4 is set to be lower than a growth temperature duringgrowth of second nitride semiconductor underlying layer 5.

(ii-3) A pressure during growth of first nitride semiconductorunderlying layer 4 is set to be higher than a pressure during growth ofsecond nitride semiconductor underlying layer 5.

(iii-3) A V/III ratio of a source material gas (a molar ratio of a groupV element with respect to a group III element in a source material gas)supplied during growth of first nitride semiconductor underlying layer 4is set to be higher than a V/III ratio of a source material gas suppliedduring growth of second nitride semiconductor underlying layer 5.

(iv-3) The number of rotations per unit time of substrate 1 duringgrowth of first nitride semiconductor underlying layer 4 is set to besmaller than the number of rotations per unit time of substrate 1 duringgrowth of second nitride semiconductor underlying layer 5.

(v-3) A volume ratio of a hydrogen gas to the total volume of a carriergas during growth of first nitride semiconductor underlying layer 4 isset to be equal to or higher than a volume ratio of a hydrogen gas tothe total volume of a carrier gas during growth of second nitridesemiconductor underlying layer 5.

Specific conditions of each of (i-3), (ii-3), (iii-3), (iv-3), and (v-3)above are shown, for example, as follows:

(i-3) A temperature of substrate 1 during growth of second nitridesemiconductor underlying layer 5 is set to 1080° C. as compared with atemperature of 1000° C. of substrate 1 during growth of first nitridesemiconductor underlying layer 4;

(ii-3) A pressure of an atmosphere during growth of second nitridesemiconductor underlying layer 5 is set to 17.3 kPa as compared with apressure of 66.6 kPa of an atmosphere during growth of first nitridesemiconductor underlying layer 4;

(iii-3) A V/III ratio of a source material gas supplied during growth ofsecond nitride semiconductor underlying layer 5 is set to 676 ascompared with a V/III ratio of 1165 of a source material gas suppliedduring growth of first nitride semiconductor underlying layer 4;

(iv-3) The number of rotations per unit time of substrate 1 duringgrowth of second nitride semiconductor underlying layer 5 is set to 1200RPM as compared with the number of rotations of 600 RPM per unit time ofsubstrate 1 during growth of first nitride semiconductor underlyinglayer 4; and

(v-3) A volume ratio of a hydrogen gas to the total volume of a carriergas ((a volume of the hydrogen gas)/(the total volume of the carriergas)) during growth of second nitride semiconductor underlying layer 5is not lower than 0.7 and not higher than 1 with respect to the volumeratio of 1 of the hydrogen gas to the total volume of the carrier gasduring growth of first nitride semiconductor underlying layer 4.

Here, when the number of rotations per unit time of substrate 1 duringgrowth of first nitride semiconductor underlying layer 4 with MOCVD withthe use of vertical MOCVD is not lower than 400 RPM and not higher than1000 RPM, a volume ratio of a hydrogen gas to the total volume of acarrier gas supplied during growth of first nitride semiconductorunderlying layer 4 is not lower than 0.7 and not higher than 1, and atleast one condition selected from the group consisting of (i-3), (ii-3),(iii-3), (iv-3), and (v-3) is satisfied, yield in an electrostaticdischarge test (an ESD test) of first nitride semiconductor underlyinglayer 4 tends to be higher. It is noted that the ESD test is conductedunder an HBM (human body model) condition in which a reverse voltage isset to 1 kV.

A method of manufacturing a nitride semiconductor element according toEmbodiment 3-1 will be described hereinafter with reference to FIGS. 12to 18. It is noted that, in the following as well, other steps maynaturally be included between steps which will be described later.

Initially, as shown in FIG. 12, n-type nitride semiconductor contactlayer 7 is formed on upper surface 5 a of second nitride semiconductorunderlying layer 5, for example, fabricated as above with MOCVD.

Then, as shown in FIG. 13, for example, with MOCVD, n-type nitridesemiconductor clad layer 9 is formed on the surface of n-type nitridesemiconductor contact layer 7.

Then, as shown in FIG. 14, for example, with MOCVD, nitridesemiconductor active layer 11 is formed on the surface of n-type nitridesemiconductor clad layer 9.

Then, as shown in FIG. 15, for example, with MOCVD, p-type nitridesemiconductor clad layer 13 is formed on the surface of nitridesemiconductor active layer 11.

It is noted that, for example, a layer obtained by doping with a p-typedopant, a group III nitride semiconductor expressed with the formulaAl_(x8)Ga_(y8)In_(z8)N (0≦x8≦1, 0≦y8≦1, 0≦z8≦1, x8+y8+z8≠0) or the like,can be employed as p-type nitride semiconductor clad layer 13 asdescribed above, however, a layer having a superlattice structureobtained by alternately stacking a layer (an A layer) composed of agroup III nitride semiconductor expressed with a formulaAl_(x8a)Ga_(1-x8a)N (0<x8a≦0.4, preferably 0.1≦x8a≦0.3) and a layer (a Blayer) composed of a group III nitride semiconductor expressed with aformula Al_(x8b)Ga_(y8b)In_(z8b)N (0≦x8≦1, 0≦y8b≦1, 0≦z8b≦1,x8b+y8b+z8b≠0) narrower in band gap than the A layer can also beemployed. It is noted that, in the superlattice structure, each of the Alayer and the B layer may be doped with a p-type dopant, or only one ofthe A layer and the B layer may be doped with a p-type dopant.

Then, as shown in FIG. 16, for example, with MOCVD, p-type nitridesemiconductor contact layer 15 is formed on the surface of p-typenitride semiconductor clad layer 13.

Then, as shown in FIG. 17, after light transmitting electrode layer 19composed, for example, of ITO (Indium Tin Oxide) is formed on thesurface of p-type nitride semiconductor contact layer 15, p-sideelectrode 21 is formed on the surface of light transmitting electrodelayer 19.

Then, as shown in FIG. 18, a part of the surface of n-type nitridesemiconductor contact layer 7 is exposed by etching away a part of astack structure after p-side electrode 21 is formed.

Then, as shown in FIG. 19, n-side electrode 20 is formed on the exposedsurface of n-type nitride semiconductor contact layer 7.

Thereafter, as shown in a schematic cross-sectional view in FIG. 40,insulating protection film 23 composed of SiO₂ or the like is formed onthe entire surface of the stack structure after n-side electrode 20 isformed, an opening is provided in insulating protection film 23 so as toexpose p-side electrode 21 and n-side electrode 20, and a wafer on whicha plurality of nitride semiconductor light emitting diode elements 500are formed is divided into individual elements, so that nitridesemiconductor light emitting diode element 500 according to Embodiment3-1 shown in FIG. 40 can be fabricated.

In nitride semiconductor light emitting diode element 500 according toEmbodiment 3-1 fabricated as above, n-type nitride semiconductor contactlayer 7, n-type nitride semiconductor clad layer 9, nitridesemiconductor active layer 11, p-type nitride semiconductor clad layer13, and p-type nitride semiconductor contact layer 15 are stacked inthis order on upper surface 5 a of second nitride semiconductorunderlying layer 5 having high crystallinity and high flatness on thesurface of first nitride semiconductor underlying layer 4 which is acontinuous film having high uniformity and continuous surfaces.

Therefore, n-type nitride semiconductor contact layer 7, n-type nitridesemiconductor clad layer 9, nitride semiconductor active layer 11,p-type nitride semiconductor clad layer 13, and p-type nitridesemiconductor contact layer 15 stacked on flat upper surface 5 a ofsecond nitride semiconductor underlying layer 5 having few crystaldefects and high crystallinity are low in dislocation density andexcellent in crystallinity.

Thus, nitride semiconductor light emitting diode element 500 accordingto Embodiment 3-1 formed of such a nitride semiconductor layer havingexcellent crystallinity is an element low in operation voltage and highin emission output.

It is noted that nitride semiconductor light emitting diode element 500fabricated under the conditions in case 3-1 was adopted as a bare chip(not sealed with resin as will be described later) evaluation element,and a current of 30 mA was fed to 10 elements. Then, it was confirmedthat an element low in operation voltage and high in emission output,which achieved light output of 39 mW, an operation voltage of 3.0 V, andan emission wavelength of 455 nm on average, was obtained.

A light emitting device 510 according to Embodiment 3-1 having aconstruction shown in FIG. 41 may be manufactured by using nitridesemiconductor light emitting diode element 500 according to Embodiment3-1.

Here, in light emitting device 510 according to Embodiment 3-1, forexample, nitride semiconductor light emitting diode element 500according to Embodiment 3-1 is set on second lead frame 31, p-sideelectrode 21 of nitride semiconductor light emitting diode element 500and first lead frame 30 are electrically connected to each other throughfirst wire 33, and n-side electrode 20 of nitride semiconductor lightemitting diode element 500 and second lead frame 31 are electricallyconnected to each other through second wire 34. Then, by molding nitridesemiconductor light emitting diode element 500 with transparent moldingresin 35, light emitting device 510 in a shape of a cannonball can bemanufactured.

Since light emitting device 510 according to Embodiment 3-1 having theconstruction shown in FIG. 41 includes nitride semiconductor lightemitting diode element 500 according to Embodiment 3-1, a light emittingdevice low in operation voltage and high in emission output can beobtained.

Embodiment 3-2

Embodiment 3-2 is characterized by being directed to a nitridesemiconductor transistor element which is an electronic device includingthe nitride semiconductor structure manufactured according to Embodiment3-1 (a stack structure of substrate 1, nitride semiconductorintermediate layer 2, first nitride semiconductor underlying layer 4,and second nitride semiconductor underlying layer 5).

FIG. 42 shows a schematic cross-sectional view of a nitridesemiconductor transistor element 600 according to Embodiment 3-2.Nitride semiconductor transistor element 600 has a nitride semiconductorstructure constituted of substrate 1 formed of a sapphire substratehaving a c plane as a main surface, in which projection portions 1 a arearranged in three equivalent directions of the a (sub) axis, as well asnitride semiconductor intermediate layer 2 composed of AlN or the like,first nitride semiconductor underlying layer 4 composed of undoped GaNor the like, and second nitride semiconductor underlying layer 5composed of undoped GaN or the like, which are successively stacked onthe surface of substrate 1.

Then, nitride semiconductor electron transit layer 71 composed ofundoped GaN or the like is stacked on flat upper surface 5 a of secondnitride semiconductor underlying layer 5 having few crystal defects andgood crystallinity, and n-type nitride semiconductor electron supplylayer 73 composed of n-type AlGaN or the like is stacked on the surfaceof nitride semiconductor electron transit layer 71.

Gate electrode 77 is provided on the surface of n-type nitridesemiconductor electron supply layer 73, and source contact layer 75S anddrain contact layer 75D composed of n-type GaN or the like are providedon respective opposing sides of gate electrode 77. In addition, sourceelectrode 78S is provided on source contact layer 75S, and drainelectrode 78D is provided on drain contact layer 75D.

One example of a method of manufacturing nitride semiconductortransistor element 600 according to Embodiment 3-2 will be describedbelow. Initially, as in Embodiment 3-1, nitride semiconductorintermediate layer 2 composed of AlN is formed with reactive sputteringon the surface of substrate 1 having projection portions 1 a and recessportions 1 b.

Then, with MOCVD under the conditions the same as in Embodiment 3-1,first nitride semiconductor underlying layer 4 composed of undoped GaNis grown on the surface of nitride semiconductor intermediate layer 2.Here, first nitride semiconductor underlying layer 4 is grown under suchconditions that two first oblique facet planes 4 r which appear in thedirection of the a (sub) axis and two first oblique facet planes 4 rwhich appear in each of the direction inclined by an angle of +60° withrespect to the direction of the a (sub) axis and the direction inclinedby an angle of −60° with respect to the direction of the a (sub) axisappear (for example, the conditions in case 3-1).

Then, second nitride semiconductor underlying layer 5 composed ofundoped GaN is grown on the surface of first nitride semiconductorunderlying layer 4 with MOCVD under the conditions the same as inEmbodiment 1. Here, second nitride semiconductor underlying layer 5 isgrown under such conditions that first oblique facet plane 4 r of firstnitride semiconductor underlying layer 4 is buried and substantiallyflat upper surface 5 a appears.

Then, with MOCVD, nitride semiconductor electron transit layer 71composed of n-type Al_(x)Ga_(1-x)N is stacked on substantially flatupper surface 5 a of second nitride semiconductor underlying layer 5 andn-type nitride semiconductor electron supply layer 73 is stacked on thesurface of nitride semiconductor electron transit layer 71.

Thereafter, as shown in FIG. 42, after source contact layer 75S anddrain contact layer 75D are formed on the surface of n-type nitridesemiconductor electron supply layer 73, source electrode 78S, drainelectrode 78D, and gate electrode 77 are each formed. Nitridesemiconductor transistor element 600 according to Embodiment 3-2 can befabricated as above.

In nitride semiconductor transistor element 600 according to Embodiment3-2 as well, as in Embodiment 3-1, nitride semiconductor layers such asnitride semiconductor electron transit layer 71 and n-type nitridesemiconductor electron supply layer 73 are stacked on upper surface 5 aof second nitride semiconductor underlying layer 5 having highcrystallinity and high flatness on the surface of first nitridesemiconductor underlying layer 4 which is a continuous film having highuniformity and continuous surfaces. Thus, since crystal defects in atwo-dimensional electron transit region at an uppermost surface ofnitride semiconductor electron transit layer 71 are decreased inparticular, electron mobility can be improved.

Therefore, in nitride semiconductor transistor element 600 according toEmbodiment 3-2 as well, each layer stacked on the surface of nitridesemiconductor intermediate layer 2 can be a layer low in dislocationdensity and excellent in crystallinity, and hence an element achievingimproved characteristics such as electron mobility can be obtained.

As above, according to the present embodiment, by forming the surface offirst nitride semiconductor underlying layer 4 which is a continuousfilm having high uniformity and continuous surfaces on substrate 1having projection portions 1 a and recess portions 1 b, upper surface 5a of second nitride semiconductor underlying layer 5 having highcrystallinity and high flatness is obtained. Thus, while occurrence ofbreakage and crack of a wafer during growth with MOCVD of a nitridesemiconductor layer stacked on such upper surface 5 a of second nitridesemiconductor underlying layer 5 and in subsequent processes issuppressed, crystallinity expressed with an X-ray half width or the likeof a nitride semiconductor layer can be improved and defect densityexpressed with the CL method, EPD, or the like can be lowered.Therefore, a nitride semiconductor element achieving improved devicecharacteristics represented by emission efficiency, electron mobility,and the like and a nitride semiconductor structure serving as a basisfor the nitride semiconductor element can be provided.

It is noted that description other than the above in Embodiments 3-1 and3-2 is the same as that in Embodiments 1-1,1-2, 2-1, and 2-2 and hencedescription thereof will not be provided.

EXAMPLES Experimental Example 1

Initially, a substrate having a diameter of 4 inches and a thickness of0.9 mm and composed of sapphire single crystal was prepared. Then, amask defining two-dimensional arrangement of projection portions shownin FIG. 3 was formed on that substrate, and the surface of the substratewas dry-etched with the use of the mask, to thereby form recess portionsin two-dimensional arrangement shown in FIG. 3.

Thus, the projection portions at the surface of the substrate werearranged in the direction of the a (sub) axis (<11-20> direction) of thesurface of the substrate and arranged in the direction inclined by +60°with respect to the direction of the a (sub) axis of the surface of thesubstrate and in the direction inclined by −60° with respect to thedirection of the a (sub) axis of the surface of the substrate. Here, inthe plan view of the surface of the substrate, the projection portionswere located at respective vertices of virtual triangle 1 t shown inFIG. 3 and periodically arranged in a direction of each side of threesides of the virtual triangle. In addition, a two-dimensional shape at abottom surface of the projection portion was annular. Moreover, in theplan view of the surface of the substrate, an interval between adjacentprojection portions was 2 μm, a diameter of an annular circle which wasthe two-dimensional shape at the bottom surface of the projectionportion was approximately 1.2 μm, and a height of the projection portionwas approximately 0.6 μm. Furthermore, the projection portion and therecess portion at the surface of the substrate each had a cross-sectionshown in FIG. 4, and the projection portion had a tip end portion.

Then, the surface of the substrate after the projection portions and therecess portions were formed was subjected to RCA cleaning. Then, thesubstrate subjected to RCA cleaning above was set in a chamber, N₂ andAr were introduced, the substrate was heated to 650° C., and a nitridesemiconductor intermediate layer having a thickness of 25 nm andcomposed of AlN crystal made of an aggregate of column crystals uniformin crystal grain extending in a direction of the normal of the surfaceof the substrate was formed on the surface of the substrate having theprojection portions and the recess portions with reactive sputteringwith which an Al target was sputtered in a mixed atmosphere of N₂ andAr.

Six wafers on which layers up to the nitride semiconductor intermediatelayer were formed as above were prepared as wafers of respective Samples1 to 6. Then, the wafers of Samples 1 to 6 were each set in the MOCVDapparatus, in the MOCVD apparatus, an ammonia gas was supplied as agroup V source material gas and TMG (trimethylgallium) was supplied as agroup III source material gas, and a third nitride semiconductorunderlying layer composed of undoped GaN crystal and having a thicknessof 300 nm was grown with MOCVD under such conditions as a growthtemperature (a temperature of a substrate during growth), a growth timeperiod, a growth pressure (a pressure in the MOCVD apparatus duringgrowth), and a V/III ratio (the number of moles of a group V sourcematerial gas supplied per unit time/the number of moles of a group IIIsource material gas supplied per unit time) shown in Table 1 below.Here, TMG was supplied into the MOCVD apparatus such that a rate ofgrowth of the third nitride semiconductor underlying layer attainedapproximately to 2 to 3 μm/h.

Then, the surface of the third nitride semiconductor underlying layergrown on the surface of each of the wafers of Samples 1 to 6 wasobserved with an SEM (Scanning Electron Microscope). FIGS. 43 to 48 showSEM images of the third nitride semiconductor underlying layers on thesurfaces of the wafers of Samples 1 to 6, respectively.

A growth parameter controlling a mode of growth of the third nitridesemiconductor underlying layer includes a growth temperature, a growthpressure, a V/III ratio, and the like, and among these, a growthparameter mainly controlling the growth mode is considered as a growthtemperature. Therefore, change in mode of growth of the third nitridesemiconductor underlying layer at the time when a temperature for growthof the third nitride semiconductor underlying layer was changed will bedescribed in further detail below.

TABLE 1 Growth Growth Time Growth Temperature Period Pressure V/III SEM[° C.] [minute] [kPa] Ratio Image Sample 1 960 1 66.7 1165 FIG. 43Sample 2 960 5 66.7 1165 FIG. 44 Sample 3 1050 1 66.7 1165 FIG. 45Sample 4 1050 5 66.7 1165 FIG. 46 Sample 5 1100 1 66.7 1165 FIG. 47Sample 6 1100 5 66.7 1165 FIG. 48

(1) Case where Growth Temperature was Set to 960° C.

First, a mode of growth of a third nitride semiconductor underlyinglayer in a case where a growth temperature was set to 960° C. wasdiscussed.

Initially, it can be seen based on comparison of FIG. 43 with FIGS. 45and 47 that, in the case where a growth time period was set to 1 minute,a uniform third nitride semiconductor layer was likely to be formed in aregion on the recess portion at the surface of the substrate when agrowth temperature was set to 960° C., which was the lowest.

Then, it is clear from FIG. 44 that, in the case where a growth timeperiod was set to 5 minutes, a third oblique facet plane of the thirdnitride semiconductor underlying layer was formed to surround an outercircumference of the projection portion of the substrate.

As shown in FIGS. 43 and 44, it was also confirmed that the recessportion at the substrate was covered with a third flat region of thethird nitride semiconductor underlying layer and the third oblique facetplane of the third nitride semiconductor underlying layer, and a ratioof area of the third flat region at the surface of the third nitridesemiconductor underlying layer was higher than a ratio of area of afirst oblique facet plane. In addition, as shown in FIGS. 43 and 44, itwas also confirmed that substantially no third nitride semiconductorunderlying layer was formed on the projection portion of the substrate.

From the foregoing, it was confirmed that the mode of growth of thethird nitride semiconductor underlying layer on the surface of each ofthe wafers of Samples 1 and 2 was the three-dimensional growth mode.

Thereafter, after a first nitride semiconductor underlying layercomposed of undoped GaN crystal and having a thickness of 1400 nm wasgrown in the three-dimensional mode on the surface of the third nitridesemiconductor underlying layer shown in each of FIGS. 43 and 44, asecond nitride semiconductor underlying layer constituted of a lowerlayer composed of undoped GaN crystal and having a thickness of 4000 nmand an upper layer composed of n-type GaN crystal doped with Si andhaving a thickness of 3000 nm was grown in the two-dimensional growthmode on the surface of the first nitride semiconductor underlying layer.It is noted that a silane gas was employed as an n-type dopant gas usedduring growth of the upper layer.

It is noted that relation among a growth temperature, a growth pressure,and a V/III ratio during growth of each of the third nitridesemiconductor underlying layer, the first nitride semiconductorunderlying layer, and the second nitride semiconductor underlying layerwas as follows.

Growth temperature: Second nitride semiconductor underlying layer>Thirdnitride semiconductor underlying layer>First nitride semiconductorunderlying layer

Growth Pressure: Second nitride semiconductor underlying layer<Thirdnitride semiconductor underlying layer<First nitride semiconductorunderlying layer

V/III ratio: Second nitride semiconductor underlying layer<Third nitridesemiconductor underlying layer<First nitride semiconductor underlyinglayer

Crystallinity of the upper surface of the second nitride semiconductorunderlying layer grown as described above was evaluated by measuring ahalf width of an X-ray rocking curve (XRC). Specifically, a half width(arcsec) of XRC at the GaN (004) plane at the upper surface of thesecond nitride semiconductor underlying layer was 30 to 40 arcsec and ahalf width of XRC at a GaN (102) plane was 110 to 120 arcsec, and itcould be confirmed that crystallinity improved as compared with theconventional example.

In addition, crystal defect density at the upper surface of the secondnitride semiconductor underlying layer was evaluated with the CL method,EPD, or the like, and it could also be confirmed that defect densitylowered as compared with the conventional example. Specifically, darkspot density obtained with the CL method and indicating crystal defectdensity at the upper surface of the second nitride semiconductorunderlying layer was not higher than 2×10⁸ cm⁻³.

(2) Case where Growth Temperature was Set to 1050° C.

Then, a mode of growth of a third nitride semiconductor underlying layerin a case where a growth temperature was set to 1050° C. was discussed.

Initially, it can be seen that, in the case of a growth time period wasset to 1 minute, as shown in FIG. 45, a third flat region and a roughsurface having many pits (a rough surface region) are both present atthe surface of the third nitride semiconductor underlying layer in theregion on the recess portion at the surface of the substrate.

Then, it can be seen that, in the case where a growth time period wasset to 5 minutes, as shown in FIG. 46, substantially the entire surfaceof the recess portion at the substrate was uniformly covered with thethird flat region of the third nitride semiconductor underlying layerand the third oblique facet plane was slightly formed around theprojection portion of the substrate.

Here, it can be seen that growth of the third nitride semiconductorunderlying layer proceeded selectively from the recess portion at thesubstrate, substantially the entire region on the recess portion at thesubstrate was uniformly covered with the third flat region of the thirdnitride semiconductor underlying layer at the time point of lapse of 5minutes since start of growth of the third nitride semiconductorunderlying layer, and the third oblique facet plane was slightly formedaround the projection portion at the substrate.

Crystallinity of the upper surface of the second nitride semiconductorunderlying layer grown as described above was evaluated by measuring ahalf width of XRC. Specifically, a half width (arcsec) of XRC at the GaN(004) plane at the upper surface of the second nitride semiconductorunderlying layer was 30 to 40 arcsec and a half width of XRC at the GaN(102) plane was 110 to 120 arcsec, and it could be confirmed thatcrystallinity improved as compared with the conventional example.

In addition, crystal defect density at the upper surface of the secondnitride semiconductor underlying layer was evaluated with the CL method,EPD, or the like, and it could also be confirmed that defect densitylowered as compared with the conventional example. Specifically, darkspot density obtained with the CL method and indicating crystal defectdensity at the upper surface of the second nitride semiconductorunderlying layer was not higher than 2×10⁸ cm⁻³.

Furthermore, warpage of the wafer after the third nitride semiconductorunderlying layer was formed was approximately from 100 to 110 μm, and nocrack was caused in the wafer surface as far as second nitridesemiconductor underlying layer 5.

(3) Case where Growth Temperature was Set to 1100° C.

A mode of growth of a third nitride semiconductor underlying layer in acase where a growth temperature was set to 1100° C. was furtherdiscussed.

Initially, it can be seen that, in the case of a growth time period wasset to 1 minute, as shown in FIG. 47, a third flat region and a roughsurface having many pits (a rough surface region) are both present atthe surface of the third nitride semiconductor underlying layer in theregion on the recess portion at the surface of the substrate.

Then, it can be seen that, in the case where a growth time period wasset to 5 minutes as well, as shown in FIG. 48, as in FIG. 47 where thegrowth time period was set to 1 minute, a third flat region and a roughsurface having many pits (a rough surface region) are both present atthe surface of the third nitride semiconductor underlying layer in theregion on the recess portion at the surface of the substrate.

Crystallinity of the upper surface of the second nitride semiconductorunderlying layer grown as described above was evaluated by measuring ahalf width of XRC. Specifically, a half width (arcsec) of XRC at the GaN(004) plane at the upper surface of the second nitride semiconductorunderlying layer was 40 to 50 arcsec and a half width of XRC at the GaN(102) plane was 110 to 120 arcsec.

In addition, crystal defect density at the upper surface of the secondnitride semiconductor underlying layer was evaluated with the CL method,EPD, or the like, and it could also be confirmed that defect densitylowered as compared with the conventional example. Specifically, darkspot density obtained with the CL method and indicating crystal defectdensity at the upper surface of the second nitride semiconductorunderlying layer was not higher than 3×10⁸ cm⁻³.

Furthermore, warpage of the wafer after the third nitride semiconductorunderlying layer was formed was approximately 120μm.

(4) Second Nitride Semiconductor Underlying Layer

The second nitride semiconductor underlying layer was grown in thethree-dimensional growth mode on the surface of the first nitridesemiconductor underlying layer shown in FIG. 46.

When the surface of the first nitride semiconductor underlying layer wasobserved, the first nitride semiconductor underlying layer had 6 firstoblique facet planes surrounding the projection portion on the outerside of the projection portion of the substrate. Here, as in the planview shown in FIG. 33, two first oblique facet planes appeared in thedirection of the a (sub) axis, and two oblique facet planes appeared ineach of the direction inclined by an angle of +60° with respect to thedirection of the a (sub) axis and the direction inclined by an angle of−60° with respect to the direction of the a (sub) axis (both of whichwere the u direction).

In addition, the first oblique facet plane had a cross-section as shownin FIG. 34, and it was a plane which similarly appeared also in adirection of depth of the cross-section shown in FIG. 34, in a rangewhere the first oblique facet planes were present. Moreover, one firstoblique facet plane surrounding the projection portion and another firstoblique facet plane surrounding the projection portion were coupled toeach other at the first flat region of the first nitride semiconductorunderlying layer.

Here, a direction of inclination of 6 first oblique facet planessurrounding the projection portion around the outer circumference of theprojection portion extended obliquely upward from an outercircumferential surface of the projection portion.

Specifically, among the 6 first oblique facet planes, in the plan viewof the surface of the first nitride semiconductor underlying layer, twofirst oblique facet planes which appeared in the direction of the a(sub) axis were inclined obliquely upward with respect to the directionof the a (sub) axis (<11-20> direction), and the facet plane extended inthat direction of inclination.

In addition, similarly, in the plan view of the surface of the firstnitride semiconductor underlying layer, two first oblique facet planeswhich appeared in each of the direction inclined by the angle of +60°with respect to the direction of the a (sub) axis and the directioninclined by the angle of −60° with respect to the direction of the a(sub) axis were also inclined obliquely upward with respect to thedirection inclined by the angle of +60° with respect to the direction ofthe a (sub) axis and the direction inclined by the angle of −60° withrespect to the direction of the a (sub) axis, and the facet planeextended in that direction of inclination.

(5) Third Nitride Semiconductor Underlying Layer

Furthermore, a second nitride semiconductor underlying layer constitutedof a lower layer composed of undoped GaN crystal and having a thicknessof 4000 nm and an upper layer composed of n-type GaN crystal doped withSi and having a thickness of 3000 nm was grown in the two-dimensionalmode on the surface of the first nitride semiconductor underlying layerabove. It is noted that a silane gas was employed as the n-type dopantgas used during growth of the upper layer.

Then, a growth temperature of the third nitride semiconductor underlyinglayer was denoted as T₁, and relation with characteristics of the secondnitride semiconductor underlying layer was examined.

FIG. 49 shows relation between T₁ and a half width (arcsec) of XRC atthe GaN (004) plane which is the upper surface of the second nitridesemiconductor underlying layer. The abscissa in FIG. 49 represents T₁ (°C.) and the ordinate in FIG. 49 represents a half width (arcsec) of XRCat the GaN (004) plane of the upper surface of the second nitridesemiconductor underlying layer.

FIG. 50 shows relation between T₁ (° C.) and warpage (μm) of a waferduring growth of the second nitride semiconductor underlying layer.Here, warpage of a wafer during growth refers to warpage of a waferimmediately before end of growth of the second nitride semiconductorunderlying layer. The abscissa in FIG. 50 represents T₁ (° C.) and theordinate in FIG. 50 represents warpage (μM) of a wafer.

As shown in FIGS. 49 and 50, when T₁ is as low as 940° C., a crack wascaused in a film at the surface of the wafer in some cases. Dataindicated with “crack” in FIGS. 49 and 50 expresses this fact. On theother hand, when T1 is as high as 1100° C., a wafer broke in some casesduring or after growth. Data indicated with “breakage” in FIGS. 49 and50 expresses this fact.

In addition, as shown in FIG. 49, as T₁ is lower, tendency that a halfwidth of XRC decreases and the second nitride semiconductor underlyinglayer having few crystal defects and a good surface is obtained isobserved.

Moreover, as shown in FIG. 50, when T₁ is too low, warpage during growthof the second nitride semiconductor underlying layer increases. This isestimated as a cause of crack in the second nitride semiconductorunderlying layer. On the other hand, when T₁ is too high, as shown inFIG. 15, third flat region 3 c and rough surface region 3 d rougher thanthird flat region 3 c are likely to be present together at the surfaceof third nitride semiconductor underlying layer 3 in the region on therecess portion. Therefore, when first nitride semiconductor underlyinglayer 4 is grown on the surface of this rough surface region 3 d, thesurface of first nitride semiconductor underlying layer 4 is more likelyto be a greater rough surface, and in second nitride semiconductorunderlying layer 5 grown further thereon, homogenous film quality isless likely to be obtained in a substrate plane and additionally thesurface does not tend to be flat. This is estimated as a cause oflikeliness of breakage of the third nitride semiconductor underlyinglayer during or after growth.

Therefore, by setting T₁ to such an extent as preventing crack in awafer, a film of good quality, which has excellent crystallinityexpressed with a half-width of XRC, is obtained for the second nitridesemiconductor underlying layer.

Setting T₁ to an appropriate value, for example, around 1050° C. andsetting a temperature T₂ for growing the first nitride semiconductorunderlying layer to an appropriate value, for example, around 1000° C.,correspond to switching the mode of growth of the first nitridesemiconductor underlying layer from the “2.5 dimensional growth mode”which is the mode of growth of the third nitride semiconductorunderlying layer as described above to the “three-dimensional growthmode.” Therefore, it is considered that an equivalent effect is obtainedalso by changing a growth pressure and a V/III ratio which areparameters other than a growth temperature.

One example of each of growth parameters including (α) a growthtemperature, (β) a growth pressure, and (γ) a V/III ratio during growthof each of the third nitride semiconductor underlying layer, the firstnitride semiconductor underlying layer, and the second nitridesemiconductor underlying layer is shown. Then, Table 2 shows relationbetween a value set as a growth parameter and a mode of growth of anitride semiconductor underlying layer.

(α) Growth temperature: The third nitride semiconductor underlying layeris grown in the 2.5 dimensional growth mode in which the third flatregion which is a flat surface and the third oblique facet planesimultaneously appear, for example, at a growth temperature of 1050° C.Then, the first nitride semiconductor underlying layer is grown in thethree-dimensional growth mode in which the first oblique facet planemainly appears, for example, with a growth temperature being lowered to960° C. Furthermore, the second nitride semiconductor underlying layeris grown in the two-dimensional growth mode in which the first obliquefacet plane is buried and a flat upper surface appears, for example,with a growth temperature being raised to 1080° C.

(β) Growth Pressure: The third nitride semiconductor underlying layer isgrown in the 2.5 dimensional growth mode in which the third flat regionwhich is a flat surface and the third oblique facet plane simultaneouslyappear, for example, at a growth pressure of 350 Torr (46.7 kPa). Then,the first nitride semiconductor underlying layer is grown in thethree-dimensional growth mode in which the first oblique facet planemainly appears, for example, with a growth pressure being raised to apressure of 500 Torr (66.7 kPa). Furthermore, the second nitridesemiconductor underlying layer is grown in the two-dimensional growthmode in which the first oblique facet plane is buried and a flat uppersurface appears, for example, with a growth pressure being lowered to apressure of 200 Torr (26.7 kPa).

(γ) V/III ratio: The third nitride semiconductor underlying layer isgrown in the 2.5 dimensional growth mode in which the third flat regionwhich is a flat surface and the third oblique facet plane simultaneouslyappear, for example, at a V/III ratio of 920. Then, the first nitridesemiconductor underlying layer is grown in the three-dimensional growthmode in which the first oblique facet plane mainly appears, for example,with a V/III ratio being raised to 1165. Furthermore, the second nitridesemiconductor underlying layer is grown in the two-dimensional growthmode in which the first oblique facet plane is buried and a flat uppersurface appears, for example, with a V/III ratio being lowered to 676.

TABLE 2 Third Nitride First Nitride Second Nitride Growth SemiconductorSemiconductor Semiconductor Parameter Underlying Layer Underlying LayerUnderlying Layer Growth 1050 960 1080 Temperature [° C.] Growth 46.766.7 26.7 Pressure [kPa] V/III 920 1165 676 Ratio Growth 2.5 DimensionalThree-Dimensional Two-Dimensional Mode Growth Mode Growth Mode GrowthMode

Relation between a growth parameter and a growth mode described above isby way of example, and a growth mode may be different depending oncombination of conditions and apparatus dependency.

Experimental Example 2 Example 1

Initially, a substrate having a diameter of 4 inches and a thickness of0.9 mm and composed of sapphire single crystal was prepared. Then, amask defining two-dimensional arrangement of projection portions shownin FIG. 3 was formed on that substrate, and the surface of the substratewas dry-etched with the use of the mask, to thereby form recess portionsin two-dimensional arrangement shown in FIG. 3.

Thus, the projection portions at the surface of the substrate werearranged in the direction of the a (sub) axis (<11-20> direction) of thesurface of the substrate and arranged in the direction inclined by +60°with respect to the direction of the a (sub) axis of the surface of thesubstrate and in the direction inclined by −60° with respect to thedirection of the a (sub) axis of the surface of the substrate. Here, inthe plan view of the surface of the substrate, the projection portionswere located at respective vertices of virtual triangle 1 t shown inFIG. 3 and periodically arranged in a direction of each side of threesides of the virtual triangle. In addition, a two-dimensional shape atthe bottom surface of the projection portion was annular. Moreover, inthe plan view of the surface of the substrate, an interval betweenadjacent projection portions was 2 μm, a diameter of an annular circlewhich is the two-dimensional shape at the bottom surface of theprojection portion was approximately 1.2 μm, and a height of theprojection portion was approximately 0.6 μm. Furthermore, the projectionportion and the recess portion at the surface of the substrate each hada cross-section shown in FIG. 4, and the projection portion had a tipend portion.

Then, the surface of the substrate after the projection portions and therecess portions were formed was subjected to RCA cleaning. Then, thesubstrate subjected to RCA cleaning above was set in a chamber, N₂ andAr were introduced, the substrate was heated to 650° C., and a nitridesemiconductor intermediate layer having a thickness of 25 nm andcomposed of AlN crystal made of an aggregate of column crystals uniformin crystal grain extending in a direction of the normal of the surfaceof the substrate was formed on the surface of the substrate having theprojection portions and the recess portions with reactive sputteringwith which an Al target was sputtered in a mixed atmosphere of N₂ andAr.

A wafer on which layers up to the nitride semiconductor intermediatelayer were formed as above was set in the vertical MOCVD apparatus, thesubstrate of the wafer was rotated at the number of rotations of 600 RPMwhile a temperature of the substrate of the wafer was heated to 1000°C., and with a pressure of an atmosphere in the vertical MOCVD apparatusbeing set to 66.6 kPa, a gas mixture of an ammonia gas which was a groupV source material gas and TMG (trimethylgallium) which was a group IIIsource material gas was supplied as a source material gas into thevertical MOCVD apparatus and only a hydrogen gas (a flow rate: 129 slm)was supplied as a carrier gas, so that undoped GaN crystal was grown for25 minutes with MOCVD to thereby form the first nitride semiconductorunderlying layer in Example 1 having a thickness of 60 nm.

Here, the source material gas was supplied such that a V/III ratio ofthe source material gas was set to 1165. It is noted that, since onlythe hydrogen gas was supplied as the carrier gas, it is clear that thevolume ratio of the hydrogen gas to the total volume of the carrier gasduring growth of the first nitride semiconductor underlying layer was 1.Then, the surface of the first nitride semiconductor underlying layer inExample 1 was observed with an SEM (Scanning Electron Microscope). FIG.51 shows an SEM image of the surface of the first nitride semiconductorunderlying layer in Example 1 having a thickness of 60 nm.

Thereafter, successively, under the conditions the same as above,undoped GaN crystal was further grown to thereby form the first nitridesemiconductor underlying layer in Example 1 having a thickness of 300nm.

Then, the surface of the second nitride semiconductor underlying layerin Example 1 was observed with the SEM. FIG. 52 shows an SEM image ofthe surface of the second nitride semiconductor underlying layer inExample 1 having a thickness of 300 nm.

Example 2

The first nitride semiconductor underlying layer in Example 2 having athickness of 60 nm was grown as in Example 1, except that a gas mixtureof a hydrogen gas (a flow rate: 129 slm) and a nitrogen gas (a flowrate: 27 slm) was supplied as a carrier gas into the vertical MOCVDapparatus. Here, a volume ratio of the hydrogen gas to the total volumeof the carrier gas during growth of the first nitride semiconductorunderlying layer in Example 2 was set to 0.83.

Then, the surface of the first nitride semiconductor underlying layer inExample 2 having a thickness of 60 nm was observed with the SEM.Consequently, at the surface of the first nitride semiconductorunderlying layer in Example 2 having a thickness of 60 nm as well, anSEM image the same as the SEM image of the surface of the first nitridesemiconductor underlying layer in Example 1 having a thickness of 60 nmshown in FIG. 51 was obtained.

Thereafter, successively, under the conditions the same as above,undoped GaN crystal was further grown to thereby form the first nitridesemiconductor underlying layer in Example 2 having a thickness of 300nm.

Then, the surface of the first nitride semiconductor underlying layer inExample 2 having a thickness of 300 nm was observed with the SEM.Consequently, at the surface of the first nitride semiconductorunderlying layer in Example 2 having a thickness of 300 nm as well, anSEM image the same as the SEM image of the surface of the first nitridesemiconductor underlying layer in Example 1 having a thickness of 300 nmshown in FIG. 52 was obtained.

Example 3

The first nitride semiconductor underlying layer in Example 3 having athickness of 60 nm was grown as in Example 1, except that a gas mixtureof a hydrogen gas (a flow rate: 129 slm) and a nitrogen gas (a flowrate: 54 slm) was supplied as a carrier gas into the vertical MOCVDapparatus. Here, a volume ratio of the hydrogen gas to the total volumeof the carrier gas during growth of the first nitride semiconductorunderlying layer in Example 3 was set to 0.7.

Then, the surface of the first nitride semiconductor underlying layer inExample 3 having a thickness of 60 nm was observed with the SEM.Consequently, at the surface of the first nitride semiconductorunderlying layer in Example 3 having a thickness of 60 nm as well, anSEM image the same as the SEM image of the surface of the first nitridesemiconductor underlying layer in Example 3 having a thickness of 60 nmshown in FIG. 51 was obtained.

Thereafter, successively, under the conditions the same as above,undoped GaN crystal was further grown to thereby form the first nitridesemiconductor underlying layer in Example 3 having a thickness of 300nm.

Then, the surface of the first nitride semiconductor underlying layer inExample 3 having a thickness of 300 nm was observed with the SEM.Consequently, at the surface of the first nitride semiconductorunderlying layer in Example 3 having a thickness of 300 nm as well, anSEM image the same as the SEM image of the surface of the first nitridesemiconductor underlying layer in Example 1 having a thickness of 300 nmshown in FIG. 52 was obtained.

Example 4

The first nitride semiconductor underlying layer in Example 4 having athickness of 60 nm was grown as in Example 1, except that the number ofrotations of the substrate was set to 400 RPM.

Then, the surface of the first nitride semiconductor underlying layer inExample 4 having a thickness of 60 nm was observed with the SEM.Consequently, at the surface of the first nitride semiconductorunderlying layer in Example 4 having a thickness of 60 nm as well, anSEM image the same as the SEM image of the surface of the first nitridesemiconductor underlying layer in Example 1 having a thickness of 60 nmshown in FIG. 51 was obtained.

Thereafter, successively, under the conditions the same as above,undoped GaN crystal was further grown to thereby form the first nitridesemiconductor underlying layer in Example 4 having a thickness of 300nm.

Then, the surface of the first nitride semiconductor underlying layer inExample 4 having a thickness of 300 nm was observed with the SEM.Consequently, at the surface of the first nitride semiconductorunderlying layer in Example 4 having a thickness of 300 nm as well, anSEM image the same as the SEM image of the surface of the first nitridesemiconductor underlying layer in Example 1 having a thickness of 300 nmshown in FIG. 52 was obtained.

Example 5

The first nitride semiconductor underlying layer in Example 5 having athickness of 60 nm was grown as in Example 1, except that the number ofrotations of the substrate was set to 1000 RPM.

Then, the surface of the first nitride semiconductor underlying layer inExample 5 having a thickness of 60 nm was observed with the SEM.Consequently, at the surface of the first nitride semiconductorunderlying layer in Example 5 having a thickness of 60 nm as well, anSEM image the same as the SEM image of the surface of the first nitridesemiconductor underlying layer in Example 1 having a thickness of 60 nmshown in FIG. 51 was obtained.

Thereafter, successively, under the conditions the same as above,undoped GaN crystal was further grown to thereby form the first nitridesemiconductor underlying layer in Example 5 having a thickness of 300nm.

Then, the surface of the first nitride semiconductor underlying layer inExample 5 having a thickness of 300 nm was observed with the SEM.Consequently, at the surface of the first nitride semiconductorunderlying layer in Example 5 having a thickness of 300 nm as well, anSEM image the same as the SEM image of the surface of the first nitridesemiconductor underlying layer in Example 1 having a thickness of 300 nmshown in FIG. 52 was obtained.

Comparative Example 1

The first nitride semiconductor underlying layer in Comparative Example1 having a thickness of 60 nm was grown as in Example 1, except that agas mixture of a hydrogen gas (a flow rate: 129 slm) and a nitrogen gas(a flow rate: 78 slm) was supplied as a carrier gas into the verticalMOCVD apparatus. Here, a volume ratio of the hydrogen gas to the totalvolume of the carrier gas during growth of the first nitridesemiconductor underlying layer in Comparative Example 1 having athickness of 60 nm was set to 0.62.

Then, the surface of the first nitride semiconductor underlying layer inComparative Example 1 having a thickness of 60 nm was observed with theSEM. FIG. 53 shows an SEM image of the surface of the first nitridesemiconductor underlying layer in Comparative Example 1 having athickness of 60 nm.

Thereafter, successively, under the conditions the same as above,undoped GaN crystal was further grown to thereby form the first nitridesemiconductor underlying layer in Comparative Example 1 having athickness of 300 nm.

Then, the surface of the first nitride semiconductor underlying layer inComparative Example 1 having a thickness of 300 nm was observed with theSEM. FIG. 54 shows an SEM image of the surface of the first nitridesemiconductor underlying layer in Comparative Example 1 having athickness of 300 nm.

Comparative Example 2

The first nitride semiconductor underlying layer in Comparative Example2 having a thickness of 300 nm was grown as in Example 1, except thatthe number of rotations of the substrate was set to 1200 RPM.

Then, the surface of the first nitride semiconductor underlying layer inComparative Example 2 having a thickness of 300 nm was observed with theSEM. FIG. 55 shows an SEM image of the surface of the first nitridesemiconductor underlying layer in Comparative Example 2 having athickness of 300 nm.

<Evaluation>

(Early Stage of Growth)

(1) First Oblique Facet Plane

As shown in FIGS. 51 and 52, in Examples 1 to 5 and Comparative Example1, in an early stage of growth of the first nitride semiconductorunderlying layer (having a thickness of 60 nm), the surface of the firstnitride semiconductor underlying layer was formed only of the firstoblique facet plane which was an r plane.

It is noted that the r plane refers to two first oblique facet planeswhich appear in the direction of the a (sub) axis as well as in each ofthe direction inclined by an angle of +60° with respect to the directionof the a (sub) axis and the direction inclined by an angle of −60° withrespect to the direction of the a (sub) axis (both of which are the udirection), as shown, for example, in FIG. 8.

(2) Surface State

As shown in FIG. 51, the first nitride semiconductor underlying layerhaving a thickness of 60 nm in each of Examples 1 to 5 was confirmed tobe a continuous film having high uniformity and continuous surfaces. Onthe other hand, as shown in FIG. 53, the first nitride semiconductorunderlying layer having a thickness of 60 nm in Comparative Example 1was confirmed to be a discontinuous film having a non-uniform surface.

(3) ESD Yield

In addition, an ESD test of the first nitride semiconductor underlyinglayer having a thickness of 60 nm in each of Examples 1 to 5 andComparative Example 1 was conducted. Consequently, yield in the ESD testof the first nitride semiconductor underlying layer in each of Examples1 to 5 was not lower than 90%. On the other hand, yield in the ESD testof the first nitride semiconductor underlying layer in ComparativeExample 1 was 20%. It is noted that the ESD test was conducted under anHBM condition in which a reverse voltage was set to 1 kV.

Thus, the reason why yield in the ESD test in Comparative Example 1 waslow is considered as follows. Namely, in a case where the first nitridesemiconductor underlying layer in an early stage of growth inComparative Example 1 is a discontinuous film, during subsequent growthof GaN crystal, a crystal defect is caused in a portion where the filmbecomes discontinuous. It has been confirmed that current leakageoriginates from this crystal defect when a nitride semiconductor lightemitting diode element is driven. It is considered that, consequently, acurrent concentrates in the vicinity of this crystal defect in the ESDtest, which has become a cause of lowering in ESD yield. Such a crystaldefect is considered as a crystal defect called micropipe, whichpropagates perpendicularly to a growth surface of GaN crystal.

(After Growth)

(1) First Oblique Facet Plane

As shown in FIGS. 52 and 54, in Examples 1 to 5 and Comparative Example1, the first oblique facet plane after growth of the first nitridesemiconductor underlying layer (having a thickness of 300 nm) was formedonly of the r plane. On the other hand, as shown in FIG. 55, inComparative Example 2, an r plane, an n plane, and a c plane weretogether present at the first oblique facet plane after growth of thefirst nitride semiconductor underlying layer (having a thickness of 300nm).

It is noted that the n plane refers to two first oblique facet planeswhich appear in each of the direction inclined by +30° with respect tothe direction of the a (sub) axis, the direction inclined by −30° withrespect to the direction of the a (sub) axis, and the direction of the m(sub) axis. In addition, the c plane is the upper surface of firstnitride semiconductor underlying layer 4.

(2) Breakage of Substrate

In Examples 1 to 5 and Comparative Example 1, no substrate broke aftergrowth of the first nitride semiconductor underlying layer having athickness of 300 nm. On the other hand, in Comparative Example 2, asubstrate broke after growth of the first nitride semiconductorunderlying layer having a thickness of 300 nm.

In an early stage of growth of the first nitride semiconductorunderlying layer (having a thickness of 60 nm) in Comparative Example 2,not only an r plane but also an n plane and a c plane were togetherpresent at the first oblique facet plane. It was thus found that, in acase where the first oblique facet planes of both of the r plane and then plane appeared, breakage was likely in the substrate after growth(having a thickness of 300 nm).

A hypothesis of this phenomenon is considered as follows. A crystalorientation of a film grown on an r plane which is the first obliquefacet plane and a crystal orientation of a film grown on an n planewhich is the first oblique facet plane are slightly displaced from eachother, which causes a line defect at an interface therebetween, and thefilm breaks along a line corresponding to a series of such line defects.Consequently, strain involved with difference in thermal expansionbetween the film and the substrate may concentrate in that portion and asubstrate may break.

(3) Half Width of XRC

Crystallinity of the first nitride semiconductor underlying layer havinga thickness of 300 nm in each of Examples 1 to 5 was evaluated bymeasuring a half width of an X-ray rocking curve (XRC). Consequently,specifically, it was confirmed that each of the GaN (004) plane and theGaN (102) plane of the surface of the first nitride semiconductorunderlying layer having a thickness of 300 nm in each of Examples 1 to 5was narrow in half width of XRC, and it was confirmed that it had highcrystallinity.

It was thus confirmed that the first nitride semiconductor underlyinglayer having a thickness of 300 nm in each of Examples 1 to 5 was higherin crystallinity than the first nitride semiconductor underlying layerhaving a thickness of 300 nm in Comparative Example 1.

(4) ESD Yield

In addition, an ESD test of the first nitride semiconductor underlyinglayer having a thickness of 300 nm in each of Examples 1 to 5 andComparative Example 1 was conducted. Consequently, yield in the ESD testof the first nitride semiconductor underlying layer in each of Examples1 to 5 was not lower than 90%. On the other hand, yield in the ESD testof the first nitride semiconductor underlying layer having a thicknessof 300 nm in Comparative Examples 1 was 20%, It is noted that the ESDtest was conducted under an HBM condition in which a reverse voltage wasset to 1 kV.

<Results>

From the results above, in the case where the first nitridesemiconductor underlying layer was grown with MOCVD with the use of thevertical MOCVD apparatus in which the carrier gas containing thehydrogen gas of which volume ratio to the total volume of the carriergas was not lower than 0.7 and not higher than 1 was used while thesubstrate was rotated at the number of rotations per unit time not lowerthan 400 RPM and not higher than 1000 RPM, as shown in Examples 1 to 5,the surface of the first nitride semiconductor underlying layer formedof a continuous film having a uniform surface and formed only of the rplane which was the first oblique facet plane was obtained.

Therefore, it is considered that a second nitride semiconductorunderlying layer having an upper surface high in crystallinity andflatness can be grown on the surface of a first nitride semiconductorunderlying layer of good quality in the embedment growth mode as inExamples 1 to 5, and a nitride layer having excellent crystallinity canbe formed above with good reproducibility on such an upper surface ofthe second nitride semiconductor underlying layer.

Consequently, a nitride semiconductor element having the first nitridesemiconductor underlying layer in each of Examples 1 to 5, such as anitride semiconductor light emitting diode element, a nitridesemiconductor laser element, and a nitride semiconductor transistorelement, is considered to have excellent characteristics.

It should be understood that the embodiments and the examples disclosedherein are illustrative and non-restrictive in every respect. The scopeof the present invention is defined by the terms of the claims, ratherthan the description above, and is intended to include any modificationswithin the scope and meaning equivalent to the terms of the claims.

The present invention can be made use of in a nitride semiconductorstructure, a nitride semiconductor light emitting element, a nitridesemiconductor transistor element, a method of manufacturing a nitridesemiconductor structure, and a method of manufacturing a nitridesemiconductor element.

In particular, the present invention can suitably be made use of in anitride semiconductor light emitting diode element used forillumination, liquid crystal backlight, display, and the like, a nitridesemiconductor laser element used for an optical disk, a projector, andthe like, a nitride semiconductor transistor element used for a portabletelephone, ultrahigh-speed optical communication, power control, and thelike, and the like.

1. A nitride semiconductor structure, comprising: a substrate having arecess portion and a projection portion provided between said recessportions at its surface; a nitride semiconductor intermediate layerprovided on said substrate; a first nitride semiconductor underlyinglayer provided on said nitride semiconductor intermediate layer; and asecond nitride semiconductor underlying layer provided on said firstnitride semiconductor underlying layer, said substrate being composed oftrigonal corundum or hexagonal crystal, said first nitride semiconductorunderlying layer having at least 6 first oblique facet planessurrounding said projection portion on an outer side of said projectionportion, said second nitride semiconductor underlying layer having alower surface in contact with said first oblique facet plane of saidfirst nitride semiconductor underlying layer, and said second nitridesemiconductor underlying layer having a flat upper surface.
 2. Thenitride semiconductor structure according to claim 1, wherein said firstoblique facet plane is inclined with respect to an m axis of a nitridesemiconductor having a hexagonal structure.
 3. The nitride semiconductorstructure according to claim 1, wherein said projection portion isarranged along a <11-20> direction of said substrate.
 4. The nitridesemiconductor structure according to claim 1, wherein in across-sectional view passing through a center of said projection portionin a plan view of said surface of said substrate, said projectionportion is in a shape having a tip end portion.
 5. The nitridesemiconductor structure according to claim 1, wherein said nitridesemiconductor intermediate layer is composed of a nitride semiconductorexpressed with a formula AlN or Al_(x)Ga_(1-x)N (0.5<x≦1).
 6. (canceled)7. A nitride semiconductor light emitting element, comprising: thenitride semiconductor structure according to claim 1; afirst-conductivity-type nitride semiconductor layer provided on saidnitride semiconductor structure; a nitride semiconductor active layerprovided on said first-conductivity-type nitride semiconductor layer; asecond-conductivity-type nitride semiconductor layer provided on saidnitride semiconductor active layer; a first electrode in contact withsaid first-conductivity-type nitride semiconductor layer; and a secondelectrode in contact with said second-conductivity-type nitridesemiconductor layer.
 8. A nitride semiconductor transistor element,comprising: the nitride semiconductor structure according to claim 1; afirst-conductivity-type nitride semiconductor electron transit layerprovided on said nitride semiconductor structure; afirst-conductivity-type nitride semiconductor electron supply layerprovided on said first-conductivity-type nitride semiconductor electrontransit layer; and an electrode provided on said first-conductivity-typenitride semiconductor electron supply layer. 9-16. (canceled)
 17. Anitride semiconductor structure, comprising: a substrate having a recessportion and a projection portion provided between said recess portionsat its surface; a nitride semiconductor intermediate layer provided onsaid substrate; a third nitride semiconductor underlying layer providedon said nitride semiconductor intermediate layer at least in said recessportion; a first nitride semiconductor underlying layer provided atleast on said third nitride semiconductor underlying layer; and a secondnitride semiconductor underlying layer provided at least on said firstnitride semiconductor underlying layer, said substrate being composed oftrigonal corundum or hexagonal crystal, a surface of said third nitridesemiconductor underlying layer having a third oblique facet plane and athird flat region, a ratio of area of said third oblique facet plane atsaid surface of said third nitride semiconductor underlying layer beinglower than a ratio of area of said third flat region, said first nitridesemiconductor underlying layer having a first oblique facet planesurrounding said projection portion, said second nitride semiconductorunderlying layer having a lower surface in contact with said firstoblique facet plane, and said second nitride semiconductor underlyinglayer having a flat upper surface.
 18. The nitride semiconductorstructure according to claim 17, wherein said first oblique facet planeincludes a plane inclined with respect to an m axis of a nitridesemiconductor having a hexagonal structure.
 19. The nitridesemiconductor structure according to claim 17, wherein said projectionportion is arranged along a <11-20> direction of said substrate.
 20. Thenitride semiconductor structure according to claim 17, wherein in across-sectional view passing through a center of said projection portionin a plan view of said surface of said substrate, said projectionportion is in a shape having a tip end portion.
 21. The nitridesemiconductor structure according to claim 17, wherein said nitridesemiconductor intermediate layer is composed of a nitride semiconductorexpressed with a formula AlN or Al_(x)Ga_(1-x)N (0.5<x≦1). 22.(canceled)
 23. A nitride semiconductor light emitting element,comprising: the nitride semiconductor structure according to claim 17; afirst-conductivity-type nitride semiconductor layer provided on saidnitride semiconductor structure; a nitride semiconductor light emittinglayer provided on said first-conductivity-type nitride semiconductorlayer; a second-conductivity-type nitride semiconductor layer providedon said nitride semiconductor light emitting layer; a first electrode incontact with said first-conductivity-type nitride semiconductor layer;and a second electrode in contact with said second-conductivity-typenitride semiconductor layer.
 24. A nitride semiconductor transistorelement, comprising: the nitride semiconductor structure according toclaim 17; a first-conductivity-type nitride semiconductor electrontransit layer provided on said nitride semiconductor structure; afirst-conductivity-type nitride semiconductor electron supply layerprovided on said first-conductivity-type nitride semiconductor electrontransit layer; and an electrode provided on said first-conductivity-typenitride semiconductor electron supply layer. 25-37. (canceled)
 38. Amethod of manufacturing a nitride semiconductor structure, comprisingthe steps of: preparing a substrate having a recess portion and aprojection portion provided between said recess portions at its surface;forming a nitride semiconductor intermediate layer on said substrate;and forming on said nitride semiconductor intermediate layer, a firstnitride semiconductor underlying layer having at least 6 first obliquefacet planes surrounding said projection portion on an outer side ofsaid projection portion with said projection portion being located in acenter, said step of forming a first nitride semiconductor underlyinglayer including the step of growing said first nitride semiconductorunderlying layer with MOCVD by using a vertical MOCVD apparatus in whicha carrier gas containing a hydrogen gas is used while said substrate isrotated, the number of rotations of said substrate per unit time beingnot lower than 400 RPM and not higher than 1000 RPM, and a volume ratioof said hydrogen gas with respect to a total volume of said carrier gasbeing not lower than 0.7 and not higher than
 1. 39. The method ofmanufacturing a nitride semiconductor structure according to claim 38,further comprising the step of forming a second nitride semiconductorunderlying layer on said first nitride semiconductor underlying layer,wherein said steps of forming a first nitride semiconductor underlyinglayer and forming a second nitride semiconductor underlying layer areeach the step of growing said first nitride semiconductor underlyinglayer and said second nitride semiconductor underlying layer with MOCVDin which a carrier gas containing a hydrogen gas is used while saidsubstrate is rotated, and performed to satisfy at least one conditionselected from the group consisting of setting a growth temperatureduring growth of said first nitride semiconductor underlying layer to belower than a growth temperature during growth of said second nitridesemiconductor underlying layer, setting a pressure during growth of saidfirst nitride semiconductor underlying layer to be higher than apressure during growth of said second nitride semiconductor underlyinglayer, setting a V/III ratio of a source material gas supplied duringgrowth of said first nitride semiconductor underlying layer to be higherthan a V/III ratio of a source material gas supplied during growth ofsaid second nitride semiconductor underlying layer, setting the numberof rotations of said substrate per unit time during growth of said firstnitride semiconductor underlying layer to be smaller than the number ofrotations of said substrate per unit time during growth of said secondnitride semiconductor underlying layer, and setting a volume ratio ofsaid hydrogen gas with respect to the total volume of said carrier gasduring growth of said first nitride semiconductor underlying layer to beequal to or higher than a volume ratio of said hydrogen gas with respectto the total volume of said carrier gas during growth of said secondnitride semiconductor underlying layer.
 40. The method of manufacturinga nitride semiconductor structure according to claim 38, wherein saidstep of preparing a substrate includes the step of forming saidprojection portion and said recess portion at a c plane of saidsubstrate or a surface inclined with respect to the c plane in a rangeof 5° or smaller.
 41. The method of manufacturing a nitridesemiconductor structure according to claim 38, wherein said substrate iscomposed of trigonal corundum or hexagonal crystal.
 42. The method ofmanufacturing a nitride semiconductor structure according to claim 38,wherein said projection portion is arranged along a <11-20> direction ofsaid substrate.
 43. The method of manufacturing a nitride semiconductorstructure according to claim 38, wherein in a cross-sectional viewpassing through a center of said projection portion in a plan view ofsaid surface of said substrate, said projection portion is in a shapehaving a tip end portion.
 44. The method of manufacturing a nitridesemiconductor structure according to claim 38, wherein said step offorming a nitride semiconductor intermediate layer includes the step offorming said nitride semiconductor intermediate layer with sputtering.45. The method of manufacturing a nitride semiconductor structureaccording to claim 38, wherein said nitride semiconductor intermediatelayer is composed of a nitride semiconductor expressed with a formulaAlN or Al_(x)Ga_(1-x)N (0.5<x≦1).
 46. A method of manufacturing anitride semiconductor element, comprising the step of forming a nitridesemiconductor layer on a surface of said second nitride semiconductorunderlying layer manufactured with the method of manufacturing a nitridesemiconductor structure according to claim 38.